CN1167104A - Fluoropropene compound, insecticide containing the same and intermediate for production thereof - Google Patents

Fluoropropene compound, insecticide containing the same and intermediate for production thereof Download PDF

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CN1167104A
CN1167104A CN97110025.XA CN97110025A CN1167104A CN 1167104 A CN1167104 A CN 1167104A CN 97110025 A CN97110025 A CN 97110025A CN 1167104 A CN1167104 A CN 1167104A
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propenyloxy
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泉惠一
池上宏
铃木雅也
坂本典保
高野仁孝
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen

Abstract

The present invention provides a fluoropropene compound represented by Formula I: wherein R1 represents a C1-C10 alkyl group or other groups, Z represents an oxygen atom or other groups, R2, R3, and R4 each independently represent a C1-C3 alkyl group or other groups, r represents an integer of 0 to 2, and X represents a halogen atom or other groups.

Description

Fluoropropene compound, insecticide containing the same and intermediate in preparation process
The technical field is as follows:
the present invention relates to a fluoropropene compound, an insecticide containing the compound, and an intermediate in the production process.
Japanese patent publication JP49-1526 (1974) describes 1- (3, 3-dichloropropyleneoxy) -4-benzyloxybenzene as an insecticide compound. However, the pesticidal activity of this compound is not always satisfactory, and therefore further development of a more suitable compound is required.
The present invention provides a fluoropropene compound (hereinafter referred to as "the present compound") of formula I as follows:
wherein R is1Represents: c1-C10Alkyl radical, C1-C5Haloalkyl, C2-C10Alkenyl radical, C2-C6Haloalkenyl, C3-C9Alkynyl, C3-C5Haloalkynyl group, C2-C7Alkoxyalkyl group, or C2-C7An alkylthio alkyl group;
C3-C6cycloalkyl radicals in which there is C1-C4An alkyl group, a carboxyl group,
C1-C3alkoxy or C1-C2A substituent of a haloalkoxy group;
C4-C9cycloalkylalkyl, wherein there may be C1-C4A substituent of an alkyl group;
C5-C6cycloalkenyl radical, where there may be C1-C4A substituent of an alkyl group;
C6-C8cycloalkenylalkyl, wherein there may be C1-C4Alkyl or Q of formula II1，Q2，Q3，Q4，Q5，Q6，Q7，Q8Or Q9The substituent (b):
wherein A represents: can have (R)16)qA phenyl group as a substituent(s),
can have (R)16)qNaphthyl as a substituent or may have (R)16)qA heterocyclic group of a substituent wherein q represents an integer of 0 to 7,
R16represents a halogen atom, a cyano group, a nitro group, a pentafluorosulfanyl group (F)5S)，(C1-C4Alkoxy) carbonyl, C1-C8Alkyl radical, C1-C3Haloalkyl, C1-C7An alkoxy group,C1-C3haloalkoxy, C1-C3Alkylthio radical, C1-C3Haloalkylthio, C1-C2Alkylsulfinyl group, C1-C2Alkylsulfonyl radical, C1-C2Haloalkylsulfinyl, C1-C2Haloalkylsulfonyl radical, C1-C2Haloalkylsulfinyl, C1-C2Haloalkylsulfonyl radical, C3-C6Alkenoxy radical, C3-C6Alkenoxy radical, C3-C6Haloalkenyloxy, C2-C4Alkenyl radical, C2-C4Haloalkenyl, C2-C4Alkynyl, C2-C4Haloalkynyl group, C3-C6Alkynyloxy, C3-C6Haloalkynyloxy, C1-C3Hydroxyalkyl radical, C2-C4Alkoxyalkyl radical, C2-C4Alkylthio alkyl, amino, dimethylamino, acetamido, acetyl, haloacetyl, formyl, carboxy, (C)1-C2Alkyl) aminocarbonyl, [ di (C)1-C2Alkyl) amino]Carbonyl group, C3-C6Cycloalkyl radical, C5-C6Cycloalkenyl radical, C3-C6Cycloalkoxy or C5-C6A cycloalkenyloxy radical, or
Phenyl, phenoxy, benzyl or benzyloxy, in whichall of them may be substituted by at least one halogen atom, C1-C4Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy and C1-C3Substituted by haloalkoxy; or
When q is an integer of 2 to 5, two adjacent R16Linked together at their terminal ends to form a trimethylene group, a tetramethylene group, a methylenedioxy group, wherein they may be substituted by halogen atoms or C1-C3Alkyl radicals, or ethylenedioxy radicals, which may be substituted by halogen atoms or by C1-C3Alkyl substituted;
b represents an oxygen atom, S (O)n，NR14A group C (═ O) G or GC (═ O) group, n represents an integer of 0 to 2, R14Represents a hydrogen atom or C1-C3An alkyl group, a carboxyl group,
g represents an oxygen atom or NR15A group; and
R15represents a hydrogen atom or C1-C3An alkyl group, a carboxyl group,
R5，R6，R7，R8and R9Each represents a hydrogen atom, C1-C3An alkyl group or a trifluoromethyl group, or a salt thereof,
R10and R11Each represents a hydrogen atom, C1-C3An alkyl group, a trifluoromethyl group or a halogen atom,
R12represents a halogen atom, C1-C4Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy or C1-C3A haloalkoxy group;
R13represents a hydrogen atom, a halogen atom or a methyl group,
i represents an integer of 0 to 6,
j represents an integer of 1 to 6,
k represents an integer of 0 to 4,
l represents an integer of 1 or 2,
m represents an integer of 0 to 2,
wherein R is1Is not 3, 3-dichloro-2-propenyl, 3, 3-dibromo-2-propenyl, or 3-bromo-3-chloro-2-propenyl;
when A is naphthyl, it may have (R)16)qA substituent group, and R16Is not 3, 3-dichloro-2-propenyloxy, 3, 3-dibromo-2-propenyloxy, or 3-bromo-3-chloro-2-propenyloxy; and
when A is phenyl, it may have Q1，Q3And Q6(R) of16)qA substituent group, and R16Is 3, 3-dichloro-2-propenyloxy, 3, 3-dibromo-2-propenyloxy or 3-bromo-3-chloro-2-propenyloxy, q is1；
Z represents an oxygen atom, a sulfur atom or NR17Wherein R is17Represents a hydrogen atom or C1-C3An alkyl group, a carboxyl group,
x represents a halogen atom;
R2，R3and R4Each represents C1-C3Alkyl radical, C1-C3A haloalkyl group, a halogen atom or a hydrogen atom, r represents an integer of 0 to 2;
wherein provided that R is2，R3And R4Not simultaneously representing a hydrogen atom.
The invention also relates to an insecticide containing the compound as an active component.
The present invention also relates to a novel compound of formula III, which is an intermediate in the preparation of a number of compounds of the present invention.
Preferred embodiments of the invention:
in the compounds of the invention, R is used1Is represented by C1-C10Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl, 1-ethylpropyl, 1, 1-dimethylhexyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl, isohexyl, 1-methylpentyl, 2-ethylbutyl, octyl, 1-methylheptyl, 1-methyloctyl, nonyl, decyl and the like.
With R1Is represented by C1-C5Examples of haloalkyl groups include trifluoromethyl, difluoromethyl, bromodifluoromethyl, 2, 2, 2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 1-fluoroethyl, 1-chloroethyl, 1-bromoethyl, 3, 3, 3, 2, 2-pentafluoropropyl, 3, 3, 3-trifluoropropyl, 1-fluoropropyl, 2-chloropropyl, 3-bromopropyl, 1,1, 2, 2, 2-pentafluoroethyl, 2-iodoethyl, 2, 2-dichloroethyl, 2-bromo-1, 1, 2, 2-tetrafluoroethyl, 2-chloro-1, 1, 2-trifluoroethyl, 2-Bromo-1, 2, 2-trifluoroethyl, 2, 2, 2-trichloroethyl, 2, 2, 2-tribromoethyl, 3-fluoropropyl, 3-chloropropyl, 3-iodoPropyl, 1,1, 2, 3, 3, 3-hexafluoropropyl, 2, 3-dibromopropyl, 2, 2, 3, 3-tetrafluoropropyl, 2-chloro-1-methylethyl, 2-bromo-1-methylethyl, 2-fluoro-1- (fluoromethyl) ethyl, 2-bromo-1- (bromomethyl) ethyl, 2-chloro-1- (chloromethyl) ethyl, 2, 2, 2-trifluoro-1- (trifluoromethyl) ethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, 4-iodobutyl, 2- (bromomethyl) propyl, 2, 2, 3, 4, 4, 4-hexafluorobutyl, 3-bromo-1- (bromomethyl) propyl, 2-chloro-2-methylpropyl, 5-fluoropentyl group, 5-chloropentyl group, 5-bromopentyl group, 5-iodopentyl group, 3-chloro-2, 2-dimethylpropyl group, 3-bromo-2, 2-dimethylpropyl group, 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl group, etc.
With R1Is represented by C2-C10Examples of alkenyl groups include vinyl, allyl, isopropenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-propenyl, 2-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-ethyl-2-propenyl, 2-ethyl-2-propenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2-methyl-2-pentenyl, 1, 3-dimethyl-2-butenyl, 1-methyl-4-pentenyl, 1-ethyl-2-butenyl, 2-ethyl-2-butenyl, 1-vinylbutyl, 2-isopropyl-2-propenyl, 2-heptenyl, 1-allyl-3-butenyl, 1-vinylhexyl, 1, 5-dimethyl-4-hexenyl, 3-nonenyl, 3-decenyl, 3, 7-dimethyl-6-octenyl and the like.
With R1Is represented by C2-C6Examples of the haloalkenyl group include 2, 2-dichlorovinyl, 2, 2-dibromovinyl, 2, 3-dichloro-2-propenyl, 2, 3-dibromo-2-propenyl, 2-chloro-2-propenyl, 3-chloro-2-propenyl, 2-bromo-2-propenyl, 3-chloro-2-butenyl, 2-chloroethenyl, 3-bromo-2-propenyl, 3, 3-dichloro-2-propenyl, 4-chloro-2-butenyl, 4, 4, 4-trifluoro-2-butenyl, 2- (chloromethyl) -2-propenyl, 3-chloro-4, 4, 4-trifluoro-2-butenyl, 4-bromo-3, 4, 4-trifluoro-2-butenyl, 3, 4, 4, 4-tetrafluoro-2-butenyl, 4, 4-dichloro-3-butenyl, 4, 4-dibromo-3-butenyl, 6, 6-dichloro-5-hexenyl and the like.
With R1Is represented by C3-C9Examples of alkynyl include 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 2-heptynyl, 3-octynyl, 1-ethynylhexyl, 3-nonynyl, 5-hexynyl and the like.
With R1Is represented by C3-C5Examples of the haloalkynyl group include 3-chloro-2-propynyl, 3-bromo-2-propynyl, 3-iodo-2-propynyl, 1-methyl-3-chloro-2-propynyl, 1-methyl-3-bromo-2-propynyl, 1-methyl-3-iodo-2-propynyl, 4-chloro-2-butynyl, 4-chloro-3-butynyl, 4-bromo-3-butynyl, 5-chloro-4-pentynyl, 5-bromo-4-pentynyl, 4-chloro-2-methyl-3-butynyl, 4-bromo-2-methyl-3-butynyl, 4-chloro-1-methyl-3-butynyl, 4-bromo-1-methyl-3-butynyl, 3-chloro-1-ethyl-2-propynyl, 3-bromo-1-ethyl-2-propynyl, and the like.
With R1Is represented by C2-C7Examples of alkoxyalkyl include methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, 2-methoxyethyl, 1-methoxyethyl, 2-ethoxyethyl, 1-ethoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 1-methoxypropyl, 2-methoxy-1-methylethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-ethoxy-2-methylethyl, 2-ethoxy-1-methylethyl, 2-methoxybutyl, 1-ethyl-2-methoxyethyl, 3-ethoxypropyl, 3-methoxybutyl, 3-methoxy-2-methylpropyl, 3-methoxy-1-methylpropyl, 2-butoxyethyl group, 3-methoxy-3-methylbutyl group, 2-butoxy-1-methylethyl group and the like.
With R1Is represented by C2-C7Examples of the alkylthioalkyl group include methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, 2-methylthioethyl, 1-methylthioethyl, 2-ethylthioethyl, 1-ethylthioethyl, 3-methylthiopropyl, 2-methylthiopropyl, 1-methylthiopropyl, 2-methylthio-1-methylethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-ethylthiopropyl, 2-ethylthio-1-methylethyl, 2-methylthiobutyl, 1-ethylthiobutyl-2-methylthioethyl, 3-ethylthiopropyl, 3-methylthiobutyl, 2-methyl-3-methylthiopropyl, 1-methyl-3-methylthiopropyl, 4-methylthiobutyl, 1-methyl-2-methylthiopropyl, 2-tert-butylthioethyl, 2-isobutylthioethyl, 2-sec-butylthioethyl, 3-tert-butylthiopropyl, 3-isobutylthiopropyl, 3-sec-butylthiopropyl and the like.
With R1Can be represented by C1-C4Alkyl radical, C1-C3Alkoxy or C1-C3C with haloalkoxy as substituent3-C6C in cycloalkyl1-C4Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
By R mentioned above1Can be represented by C1-C4Alkyl radical, C1-C3Alkoxy or C1--C3C with haloalkoxy as substituent3-C6C in cycloalkyl1-C3Examples of alkoxy groups include methoxy, ethoxy, propoxy or isopropoxy.
By R mentioned above1Can be represented by C1-C4Alkyl radical, C1-C3Alkoxy or C1-C3C with haloalkoxy as substituent3-C6C in cycloalkyl1-C3Examples of haloalkoxy groups include trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, 2, 2, 2-trifluoroethoxy, 2, 2, 2, 1, 1-pentafluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-chloro-1, 1, 2-trifluoroethoxy, 2-bromo-1, 1, 2-trifluoroethoxy, 1,1, 2, 2-tetrafluoroethoxy, 3, 3, 3, 2, 2, 1-hexafluoropropoxy, and the like.
With R1Can be represented by C1-C4Alkyl radical, C1-C3Alkoxy or C1-C3C substituted by haloalkoxy3-C6Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
With R1Can be represented by C1-C4C substituted by alkyl4-C9C in cycloalkyl1-C4Alkyl includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl. With R1Can be represented by C1-C4C substituted by alkyl4-C9C in cycloalkylalkyl4-C9Examples of cycloalkylalkyl groups of (a) include cyclopropylmethyl, 1-cyclopropylethyl, 2-cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl, 2-cyclopentylethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl and the like.
With R1Can be represented by C1-C4C substituted by alkyl5-C6C in cycloalkenyl1-C4Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
With R1Can be represented by C1-C4C substituted by alkyl5-C6Examples of cycloalkenyl groups include 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl or 3-cyclohexenyl.
With R1Can be represented by C1-C4C substituted by alkyl6-C8C in cycloalkenylalkyl1-C4Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl.
With R1Can be represented by C1-C4C substituted by alkyl6-C8Examples of cycloalkenylalkyl groups include 1-cyclopentenylmethyl, 2-cyclopentenylmethyl, 3-cyclopentenylmethyl, 1-cyclohexenylmethyl,2-cyclohexenylmethyl, 3-cyclohexenylmethyl, 2- (3-cyclohexenyl) ethyl and the like.
With R2，R3，R4，R10，R11，R12，R13X and R16The halogen atom includes fluorine, chlorine, bromine and iodine atoms.
With R12Is represented by C1-C4Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butyl.
R16Is represented by C1-C8Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, heptyl 1, 1-dimethylhexyl, 1-methylbutyl, 2-methylbutyl, 1, 2-dimethylpropyl, isohexyl, 1-methylpentyl, 2-ethylbutyl, octyl, 1-methylheptyl and the like.
With R2，R3，R4，R12And R16Is represented by C1-C3Haloalkyl includes trifluoromethyl, trichloromethyl, difluoroethyl, bromodifluoromethyl, 2, 2, 2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 1-fluoroethyl, 1-chloroethyl, 1-bromoethyl, 3, 3, 3, 2, 2-pentafluoropropyl, 3, 3, 3-trifluoropropyl, 1-fluoropropyl, 2-chloropropyl, 3-bromopropyl and the like.
With R12Is represented by C1-C3Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, and the like.
With R12And R16Is represented by C1-C3Haloalkoxy includes trifluoromethoxy, difluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-chloro-1, 1, 2-trifluoroethoxy, 2-bromo-1, 1, 2-trifluoroethoxy, 1,1, 2, 2-tetrafluoroethoxy, 3, 3, 3, 2, 2, 1-hexafluoropropoxy, 3-fluoropropoxy, 3-chloropropoxy, 3-bromopropoxy, 3, 3, 3, 2, 2-pentafluoropropoxy, 3, 3, 3-trifluoropropoxy, 2, 2, 2, 1, 1-pentafluoroethoxy, 3, 3, 2, 1, 1-hexafluoropropoxy, and the like.
With R2、R3、R4、R5、R6、R7、R8、R9、R10、R17、R11、R14And R15Is represented by C1-C3Alkyl radicalExamples of (b) include methyl, ethyl, propyl or isopropyl.
With R16Is represented by C1-C7Examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, isobutoxy, pentyloxy, isopentyloxy, 1-methylbutyloxy, 1-ethylpropoxy, neopentyloxy, tert-pentyloxy, 1, 2-dimethylpropoxy, hexyloxy, heptyloxy and the like.
With R16Is represented by C1-C3Examples of alkylthio groupsinclude methylthio, ethylthio, propylthio, isopropylthio and the like.
With R16Is represented by C1-C3Examples of haloalkylthio include trifluoromethylthio, difluoromethylthio, bromodichloromethylthio, 2, 2, 2-trifluoroethylthio, 2-chloro-1, 1, 2-trifluoroethylthio, 2-bromo-1, 1, 2-trifluoroethylthio, 1,1, 2, 2-tetrafluoroethylthio, 2-chloroethylthio, 2-fluoroethylthio, 2-bromoethylthio, 1,1, 2, 2, 2-pentafluoroethylthio, 3-fluoropropylthio, 3-chloropropylthio, 3-bromopropylthio, 3, 3, 3, 2, 2-pentafluoropropylthio, 3, 3, 3-trifluoropropylthio and the like.
With R16Is represented by C3-C6Examples of the alkenyloxy group include allyloxy group, 2-methyl-2-propenyloxy group, 1-methyl-2-propenyloxy group, 2-butenyloxy group, 3-methyl-2-butenyloxy group, 2-pentenyloxy group, 2-hexenyloxy group and the like.
With R16Is represented by C3-C6Haloalkenyloxy includes 3, 3-dichloro-2-propenyloxy, 3, 3-dibromo-2-propenyloxy, 2, 3-dichloro-2-propenyloxy, 2, 3-dibromo-2-propenyloxy, 2-chloro-2-propenyloxy, 3-chloro-2-propenyloxy. 2-bromo-2-propenyloxy, 3-fluoro-3-chloro-2-propenyloxy, 3-methyl-4, 4, 4-trifluoro-2-butenyloxy, 3-chloro-2-butenyloxy and the like.
With R16Is represented by C2-C4Examples of alkenyl groups include vinyl, isopropenyl, 1-propenyl, 2-methyl-1-propenyl, 1-methyl-propenyl, allyl, 1-methyl-2-propenyl, 2-butanylAlkenyl groups, and the like.
With R16Is represented by C2-C4Examples of haloalkenyl groups include 2, 2-dichloroethenyl, 2, 2-dibromoethenyl, 3, 3-dichloro-2-propenyl, 3, 3-dibromo-2-propenyl, 2, 3-dichloro-2-propenyl, 2, 3-dibromo-2-propenyl, 2-chloro-2-propenyl, 3-chloro-2-propenyl, 2-bromo-2-propenyl, 3-chloro-2-butenyl and the like.
With R16Is represented by C2-C4Examples of alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-methyl-2-propynyl, and the like.
With R16Is represented by C2-C4Examples of the haloalkynyl group include a chloroethynyl group, a bromoethynyl group, an iodoethynyl group, a 3-chloro-2-propynyl group, a 3-bromo-2-propynyl group, a 3-iodo-2-propynyl group, a 1-methyl-3-chloro-2-propenyl group, a 1-methyl-3-bromo-2-propynyl group, a 1-methyl-3-iodo-2-propynyl group and the like.
With R16Is represented by C2-C4Examples of alkoxyalkyl groups include methoxymethyl, ethoxymethylAnd (C) a group such as propoxymethyl group, isopropoxymethyl group, 2-methoxyethyl group, 1-methoxyethyl group, 2-ethoxyethyl group, 1-ethoxyethyl group, 3-methoxypropyl group, 2-methoxypropyl group, 1-methoxypropyl group, 2-methoxy-1-methylethyl group and the like.
With R16Is represented by C2-C4Examples of the alkylthioalkyl group include methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl, 2-methylthiomethyl, 1-methylthioethyl, 2-ethylthioethyl, 1-ethylthioethyl, 3-methylthiopropyl, 2-methylthiopropyl, 1-methylthiopropyl, 2-methylthio-1-methylethyl and the like.
With R16Is represented by C3-C6Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
With R16Is represented by C5-C6Examples of cycloalkenyl groups include 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl and the like.
With R16Is represented by C3-C6Examples of the cycloalkoxy group include cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy and the like.
With R16Is represented by C5-C6Examples of the cycloalkenyloxy group include a 1-cyclopentenyloxy group, a 2-cyclopentenyloxy group, a 3-cyclopentenyloxy group, a 1-cyclohexenyloxy group, a 2-cyclohexenyloxy group, a 3-cyclohexenyloxy group and the like.
With R16Is represented by C1-C2Examples of the alkylsulfinyl group include a methylsulfinyl group or an ethylsulfinyl group.
With R16Is represented by C1-C2Examples of alkylsulfonyl include methylsulfonyl or ethylsulfonyl.
With R16Is represented by C1-C2Examples of haloalkylsulfinyl include trifluoromethylsulfinyl, 2, 2, 2-trifluoroethylsulfinyl, perfluoroethylsulfinyl and the like.
With R16Is represented by C1-C2Examples of haloalkylsulfonyl groups include trifluoromethylsulfonyl, 2, 2, 2-trifluoroethylsulfonyl, perfluoroethylsulfonyl and the like.
With R16Is represented by (C)1-C2Alkyl) aminocarbonyl groups include methylaminocarbonyl or ethylaminocarbonyl.
With R16Is represented by C1-C3Examples of hydroxyalkyl groups include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, and the like.
With R16Is represented by [ di (C)1-C2Alkyl) amino]Examples of the carbonyl group include dimethylaminocarbonyl group, N-methyl-N-ethylaminocarbonyl group, diethylaminocarbonyl group and the like.
With R16May be represented by a halogen atom, C1-C4Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy or C1-C3C in phenyl, phenoxy, benzyl, benzyloxy substituted by haloalkoxy1-C4Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, sec-butylButyl tert-butyl or isobutyl, and the like.
With R16May be represented by a halogen atom, C1-C4Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy or C1-C3C in phenyl, phenoxy, benzyl or benzyloxy substituted by haloalkoxy1-C3Examples of haloalkyl groups include trifluoromethyl, difluoromethyl, bromodifluoromethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-fluoroethyl, 2-bromoethyl, 1-fluoroethyl, 1-chloroethyl, 1-bromoethyl, 3, 3, 3, 2, 2-pentafluoropropyl, 3, 3, 3-trifluoropropyl, 1-fluoropropyl, 2-chloropropyl, 3-bromopropyl and the like.
With R16May be represented by a halogen atom, C1-C4Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy or C1-C3C in phenyl, phenoxy, benzyl, benzyloxy substituted by haloalkoxy1-C3Examples of alkoxy groups include methoxy, ethoxy, propoxy or isopropoxy.
With R16May be represented by a halogen atom, C1-C4Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy or C1-C3C in phenyl, phenoxy, benzyl, benzyloxy substituted by haloalkoxy1-C3Examples of haloalkoxy include trifluoromethoxy, difluoromethoxy, bromodichloromethoxy, 2-fluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-chloro-1, 1, 2-trifluoroethoxy, 2-bromo-1, 1, 2-trifluoroethoxy, 1,1, 2, 2-tetrafluoroethoxy, 3, 3, 3, 2, 2, 1-hexafluoropropoxy, 3-fluoropropoxy, 3-chloropropoxy, 3-bromopropoxy, 3, 3, 3, 2, 2-pentafluoropropoxy, 3, 3, 3-trifluoropropoxy, 2, 2, 1, 1-pentafluoroethoxy and the like.
With R16Represents a methylenedioxy group which may be substituted by a halogen atom or an ethylenedioxy group which may be substituted by a halogen atom by terminating two adjacent R groups16Is connected toTogether and q is 2 to 5, wherein examples of the halogen atom include fluorine, chlorine, bromine, iodine atom.
With R16Can be represented by C1-C3Methylenedioxy substituted by alkyl or optionally substituted by C1-C3Ethylenedioxy substituted by alkyl groups by terminating two adjacent R groups16Are linked together to form a complex and have a q value of 2 to 5, wherein C1-C3Examples of alkyl groups include methyl; ethyl, propyl, or isopropyl.
Examples of the optionally substituted heterocyclic group represented by A may include isoxazole, isothiazole, thiazole, 1, 3, 4-thiadiazole, pyrrole, furan, thiophene, pyrazole, imidazole, 1, 2, 3-triazole, 1, 2, 4-triazole, 1, 2, 3, 4-tetrazole, pyridine, pyridazine, pyrimidine, pyrazine, 1, 2, 4-triazine, 1, 3, 5-triazine, indole, benzofuran, thianaphthene, indazole, benzimidazole, benzotriazole, benzisoxazole, benzoxazole, benzothiazole, quinoline, isoquinoline, quinoxaline, quinazoline, piperidine, piperazine, tetrahydrofuran, tetrahydropyran, pyrazoline and the like.
In the compounds of the invention, R1Preferred embodiments of (a) include:
Q1and A is phenyl, which may be substituted by (R)16)qIs substituted or can be substituted by (R)16)q(ii) a substituted 2-pyridyl group,
Q2and A is optionally substituted (R)16)qSubstituted phenyl, or can be substituted by (R)16)q(ii) a substituted 2-pyridyl group,
Q3and A is optionally substituted (R)16)qSubstituted phenyl, or can be substituted by (R)16)q(ii) a substituted 2-pyridyl group,
Q4，Q5，Q6，Q7，Q8or Q9And A is optionally substituted (R)16)qSubstituted phenyl, or can be substituted by (R)16)qSubstituted 2-pyridyl.
Preferred embodiments of Z are oxygen atoms or sulfur atoms, and more preferred embodiments are oxygen atoms.
Preferred embodiments of B are oxygen atoms, CO2Or CONH group.
Preferred embodiments of X are a chlorine atom and a bromine atom.
Among the compounds of the present invention, examples of preferred compounds thereof are:
a compound wherein R1Is Q1Wherein A is optionally substituted (R)16)qSubstituted phenyl, or can be substituted by (R)16)qSubstituted 2-pyridyl; z is an oxygen atom, R is O, X is a chlorine or bromine atom, R2And R3Not both represent a hydrogen atom;
a compound wherein R1Is Q2Wherein A is optionally substituted (R)16)qSubstituted phenyl, or can be substituted by (R)16)qSubstituted 2-pyridyl, Z being an oxygen atom, R5，R6And R7Each represents a hydrogen atom, i is an integer of 0 to 3, R is 0, x is a chlorine or bromine atom, R is a hydrogen atom2And R3Not both represent a hydrogen atom; and
a compound wherein R1Is Q3Wherein A is optionally substituted (R)16)qSubstituted phenyl, or can be substituted by (R)16)qSubstituted 2-pyridyl group, Z being an oxygen atom, B being an oxygen atom, CO2Radicals or CONH radicals, R5、R6And R7Each represents a hydrogen atom, i is an integer of 2 or 3; r is 0, x is a chlorine or bromine atom, R2And R3Not both represent hydrogen atoms.
In preferred compounds, R16More preferably a halogen atom, C1-C3Haloalkyl, C1-C4Alkoxy or C1-C3A haloalkoxy group; r2And R3Each represents C1-C3Alkyl, C1-C3Haloalkyl (e.g. trifluoromethyl) or halogen atoms, wherein R2And R3More preferably represents C1-C2Alkyl, trifluoromethyl or halogen atom.
The compounds of the invention may be prepared according to methods a through G.
Method A
A compound of formula I, when R1Is not Q1And Z is an oxygen atom, can be prepared by the method A.
Process A for preparing a compound of formula I comprising reacting an alcohol of formula IV wherein R1As defined above:
R1OH
with a compound of formula III:wherein R is2，R3，R4R and x are as defined above.
The above reaction is preferably carried out in an inert solvent in the presence of a suitable dehydrating agent.
Examples of the dehydrating agent used include dicyclohexylcarbodiimide, dialkyl (e.g., C)1-C4) Azodicarboxylic acid esters (e.g., diethyl azodicarboxylate, diisopropyl azodicarboxylate, etc.), trialkyl (e.g., C)1-C20) Phosphine, or triarylphosphine (e.g., triphenylphosphine, trioctylphosphine, tributylphosphine, etc.) or the like.
Examples of the above solvent include hydrocarbons such as benzene, xylene, toluene and the like; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and the like; or hydrocarbon halides such as carbon tetrachloride, methylene chloride, chlorobenzene, dichlorobenzene, and the like.
The reaction temperature is usually in the range of-20 ℃ to 200 ℃ or the boiling temperature of the solvent used.
The molar ratio of the compounds of the formulae III and IV, and of the dehydrating agent used in the reaction, may be suitably matched. However, it is preferable that the amount used in the above reaction is an equimolar ratio or substantially equimolar ratio.
After completion of the reaction, the reaction solution may be subjected to conventional post-treatments including organic solvent extraction, concentration and the like to isolate the desired compound of the present invention. If desired, the resulting compound may be further purified by methods such as chromatography, distillation, and recrystallization.
Method B
Process B for preparing a compound of formula I comprises reacting a halide represented by formula V:
R1-L1
in the formula1As defined above, L1Represents a halogen atom (e.g., chlorine, bromine or iodine atom, etc.), a methanesulfonyloxy group or a toluenesulfonyloxy group,
with a compound of formula VI:
formula (III) Z, R2、R3、R4R and X are as defined above.
The above reaction is preferably carried out in an inert solvent in the presence of a suitable base.
Examples of the above-mentioned solvent to be used include ketones such as acetone, methyl ethyl ketone, cyclohexanone; ethers, e.g. 1, 2-dimethoxyethane, tetrahydrofuran, dioxane, dialkyl (e.g. C)1-C4) Ethers (e.g., diethyl ether, diisopropyl ether, etc.); polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, acetonitrile, nitromethane, and the like; halogenated hydrocarbons such as dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, etc.; hydrocarbons such as xylene, benzene, toluene, etc.; or water, etc. A mixed solvent thereof may be optionally used.
Examples of the base used in the above reaction include hydroxides of alkali metals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; carbonates of alkali metals or alkaline earth metals such as lithium carbonate, potassium carbonate, sodium carbonate, calcium carbonate and the like; hydrides of alkali metals or alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride, calcium hydride and the like; alkali metal alkoxides (e.g. C)1-C4) Such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.; and organic bases such as triethylamine, pyridine, and the like.
A catalyst, such as an ammonium salt (e.g., triethylbenzylammonium chloride, etc.), may also be added to the above reaction in an amount of 0.01 to 1 mole relative to 1 mole of the compound of formula VI.
The reaction temperature is controlled in the range of from-20 ℃ to the boiling temperature of the solvent used, or 150 ℃, preferably in the range of from-5 ℃ to the boiling temperature of the solvent used, or 100 ℃.
The molar ratio of the compounds of formulae V and VI and the base used in the reaction may be suitably matched, but it is preferred that they are used in equimolar or substantially equimolar proportions.
After completion of the reaction, the reaction solution may be subjected to conventional post-treatments including organic solvent extraction, concentration and the like to isolate the desired compound of the present invention, and if necessary, the resulting compound may be further purified by chromatography, distillation, recrystallization and the like.
Method C
Process C for preparing the compound of formula I comprises reacting an aldehyde compound of formula VII:
Figure A9711002500211
in the formula1，R2，R3，R4And r and Z are as defined above,
with a halogen compound of the following formula VIII and a trialkylphosphine, triarylphosphine or tri (alkylamino) phosphine:
CF2X2，CFX3，CF2XC (-O) -ONa or CFX2C(＝O)-ONa
Wherein X is as defined above.
The above reaction can be carried out in an inert solvent, and if necessary, the reaction can be carried out in the presence of metallic zinc.
Examples of the inert solvent used include hydrocarbons such as benzene, xylene, toluene and the like; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, and the like; hydrocarbon halides such as dichloromethane, 1, 2-dichloroethane, chlorobenzene, etc. (excluding carbon tetrabromide and carbon tetrachloride), and mixed solvents thereof.
The reaction temperature is controlled in the range from-30 ℃ to the boiling temperature of the solvent used or to 200 ℃.
(trialkyl C) as described above1-C20) Examples of phosphines, triarylphosphines or tri (alkylamino) phosphines include triphenylphosphine, trioctylphosphine, tris (dimethylamino) phosphine, and the like. If metallic zinc is used as required, it is preferable to use finely ground zinc particles, such as metallic zinc powder.
The molar ratio of the compounds of the formulae VII and VIII used in the reaction can be suitably matched, and when 1 mole of the aldehyde of the formula VII is used, 1 to 5 moles of the halogen compound of the formula VIII and 2 to 10 moles of trialkylphosphine, triallylphosphine or tris (alkylamino) phosphine can be used.
If zinc is used, 1 to 5 moles of zinc can be used relative to 1 mole of the aldehyde of formula VII.
The reaction is preferably carried out in substantially similar proportions as described above.
After the completion of the reaction, the reaction solution may be subjected to a conventional post-treatment. Including extraction with organic solvents, concentration, etc., to isolate the desired compound of the invention. If necessary, the resulting compound may be further purified by chromatography, distillation, recrystallization, or the like.
Method D
In formula I, R is 0 if Z1-Q3Or Q4，B＝B1(B1Represents an oxygen atom, a sulfur atom or NR14And R is14As defined above), can be prepared using the D method.
A process D for preparing a compound of formula I, comprising reacting a compound of formula IX:
Figure A9711002500221
in the formula R2，R3，R4，r，B1，R5，R6，R7I and x are as defined above,
with a compound of formula X: A-L1Or
Figure A9711002500231
In the formula, A, R8，R9，L1And j is as defined above.
The above reaction is preferably carried out in an inert solvent in the presence of a suitable base.
Examples of the solvent used include ketones such as acetone, methyl ethyl ketone, cyclohexanone and the like; ethers, e.g. 1, 2-dimethoxyethane, tetrahydrofuran, dioxane, dialkyl (e.g. C)1-C4) Ethers (e.g., diethyl ether, diisopropyl ether, etc.); polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, acetonitrile, nitromethane, and the like; hydrocarbon halides such as dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, etc.; hydrocarbons such as toluene, benzene, xylene, etc.; or water, etc. A mixed solvent thereof may also be used.
Examples of the base used include hydroxides of alkali metals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; carbonates of alkali metals or alkaline earth metals such as lithium carbonate, potassium carbonate, sodium carbonate, calcium carbonate and the like; hydrides of alkali metals or alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride, calcium hydride and the like; alkoxides of alkali metals (C)1-C4) Such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.; and organic bases such as triethylamine, pyridine, and the like.
Optionally, a catalyst, such as an ammonium salt (e.g., triethylbenzylammonium chloride, etc.), may be added to the reaction in an amount of 0.01 to 1 mole relative to 1 mole of the compound of formula IX.
The reaction temperature is controlled in the range from-20 ℃ to the boiling temperature of the solvent used or to 150 ℃, preferably in the range from-5 ℃ to the boiling temperature of the solvent used or to 100 ℃.
The molar ratio of the compounds of the formulae IX and X and the base used in the reaction can be suitably matched, preferably in an equimolar or substantially equimolar ratio in the amount used in the reaction.
After the completion of the reaction, the reaction solution may be subjected to a conventional post-treatment. Including organic solvent extraction, concentration, etc., to isolate the desired compound of the present invention, and, if desired, further purification of the resulting compound by chromatographic separation, distillation, recrystallization, etc.
Method E
The invention relates to compounds of the formula I, wherein R is H, O1＝Q3，Q4，Q7Or Q8In this case, the preparation can be carried out by the method E.
Process E for preparing the compounds of formula I of the present invention comprises reacting an alcohol compound of formula XI:
Figure A9711002500241
in the formula R2，R3，R4，R5，R6、R7R, i and X are as defined above.
With a compound of formula XII:
Figure A9711002500242
or A-C- (R)10)＝C(R11)-COOH
Q81
The reaction is preferably carried out in an inert solvent in the presence of a suitable dehydrating agent.
Examples of the dehydrating agent used include dicyclohexylcarbodiimide, dialkyl (e.g., C)1-C4) Azo compoundsDicarboxylic acid esters (e.g., diethyl azodicarboxylate, diisopropyl azodicarboxylate, etc.), trialkyl (e.g., C)1-C20) Phosphines or triarylphosphines (e.g., triphenylphosphine, trioctylphosphine, tributylphosphine, etc.).
Examples of the solvent used include hydrocarbons such as benzene, xylene, toluene; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and the like; or hydrocarbon halides such as carbon tetrachloride, methylene chloride, chlorobenzene, dichlorobenzene, etc., and mixed solvents thereof may also be used.
The reaction temperature is controlled in the range from-20 ℃ to 200 ℃ or to the boiling temperature of the solvent used.
The molar ratios of the dehydrating reagent and the compounds of the formulae XI and XII used in the reaction can be suitably matched, but they are preferably used in equimolar or substantially equimolar ratios.
After the completion of the reaction, the reaction solution may be subjected to a conventional post-treatment. Including organic solvent extraction, concentration, etc., to isolate the desired compound of the invention. If necessary, the resulting compound may be further purified by a chromatographic separation method, distillation, recrystallization, or the like.
Method F
In formula I, if Z ═ O, B ═ O, S, NR14，C(＝O)O，R1＝Q3，Q4，Q7Or Q8Such compounds may be prepared by process F.
Process F for preparing a compound of formula I comprises reacting a compound of formula XIII:
Figure A9711002500251
in the formula2，R3，R4，r，R5，R6，R7，X，L1And i is as defined above,
with a compound of formula XIV:
Figure A9711002500261
in the formula8，R9，R10，R11A, B and j are as defined above.
The above reaction is preferably carried out in an inert solvent in the presence of a suitable base.
Examples of the solvent used include ketones such as acetone, methyl ethyl ketone, cyclohexanone and the like, ethers such as 1, 2-dimethoxyethane, tetrahydrofuran, dioxane, dialkyl (e.g., C)1-C4) Ethers (e.g., diethyl ether, diisopropyl ether, etc.); polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoric triamide, sulfolane, acetonitrile, nitromethane, and the like; hydrocarbon halides such as dichloromethane, chloroform, 1, 2-dichloroethane, chlorobenzene, etc.; hydrocarbons such as toluene, benzene, xylene, etc.; or water, etc. The above-mentioned mixed solvent may be used.
Examples of the base to be used include hydroxides of alkali metals or alkaline earth metals, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; carbonates of alkali metals or alkaline earth metals such as lithium carbonate, potassium carbonate, sodium carbonate, calcium carbonate and the like; hydrides of alkali metals or alkaline earth metals, such as lithium hydride, sodium hydride, potassium hydride, calcium hydride and the like; alkoxides of alkali metals (e.g. C)1-C4) Such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, etc.; and organic bases such as triethylamine, pyridine, etc. A catalyst, such as an ammonium salt (e.g., triethylbenzylammonium chloride, etc.), may also be added to the reaction, relative to 1 mole of the compound of formula XIVThe amount of the addition of the oxidizing agent is 0.01 to 1 mol.
The reaction temperature may be controlled in the range from-20 ℃ to the boiling temperature of the solvent used or to 150 ℃, and preferably in the range from-5 ℃ to the boiling temperature of the solvent used or to 100 ℃.
The molar ratio of the raw materials and the base used in the reaction may be appropriately matched. Preferably, the amount used in the reaction is in an equimolar ratio or substantially equimolar ratio.
After completion of the reaction, the reaction solution may be subjected to conventional post-treatments including organic solvent extraction, concentration and the like. To isolate the desired compound of the invention. If necessary, the resulting compound may be further purified by a chromatographic separation method, distillation, recrystallization, or the like.
In formula I, if Z ═ O, B ═ C (═ O) NR15，R1＝Q3Or Q4Then the compounds can be prepared by process G.
Method G
A G process for preparing a compound of formula I comprises reacting an amino compound of formula XV:
Figure A9711002500271
in the formula R2，R3，R4，R5，R6，R7，R15R, X and i are as defined above,
and is provided withReacting a carboxylic acid compound of formula XVI:
Figure A9711002500281
in the formula, A, R8，R9And j is as defined above.
The above reaction is preferably carried out in an inert solvent in the presence of a suitable dehydrating agent.
Examples of the dehydrating agent used include dicyclohexylcarbodiimide, dialkyl (e.g., C)1-C4) Azodicarboxylic acid esters (e.g., diethyl azodicarboxylate, diisopropyl azodicarboxylate, etc.), trialkyl (e.g., C)1-C20) Phosphines or triarylphosphines (e.g., triphenylphosphine, trioctylphosphine, tributylphosphine, etc.).
Examples of the solvent used include hydrocarbons such as benzene, xylene, toluene and the like; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and the like; or hydrocarbon halides such as carbon tetrachloride, methylene chloride, chlorobenzene, dichlorobenzene, and the like.
The reaction temperature is preferably controlled in the range from-20 ℃ to 200 ℃ or to the boiling temperature of the solvent used.
The molar ratio of the starting material to the dehydrating solvent used in the reaction may be suitably matched, and it is preferable that the amount used in the reaction is an equimolar ratio or substantially equimolar ratio.
After completion of the reaction, the reaction solution may be subjected to conventional post-treatments including organic solvent extraction, concentration and the like. To isolate the desired compound of the present invention, and if necessary, further purifying the resulting compound by chromatography, distillation, recrystallization, or the like.
If the compound has an asymmetric atom, the compounds of the present invention correspondingly include optionally active isomers (e.g., (+) isomer, (-) isomer, etc.) having biological activity, as well as compounds containing isomers in any ratio. If the compound has geometric isomers, the compound of the present invention correspondingly includes optional active isomers having biological activity (e.g., cis-isomer, trans-isomer), and compounds containing isomers in any ratio.
Furthermore, the following formulae XVII to XXI (substituent R)1The same meaning is shown in tables 1 to 20) represent examples of the compounds of the present invention, but this does not constitute a limitation of the compounds of the present invention.Formula XVIIFormula XVIIChemical formula XIXChemical formula XX
Figure A9711002500331
Chemical formula XXIFormula XXI-sequence
Figure A9711002500351
TABLE 1R1R1CH3CH3(CH2)6CH(CH3)C2H5CH3(CH2)7CH2CH3CH2CH2CH3(CH2)6CH2(CH3)2CH CF3CH3(CH2)2CH2CHF2(CH3)2CHCH2CF2BrCH3CH2CH(CH3) CF3CH2(CH3)3C CF3CF2CH3(CH2)3CH2FCH2CH2(CH3)2CHCH2CH2ClCH2CH2(CH3)3CCH2BrCH2CH2CH3(CH2)2CH(CH3) ICH2CH2CH3CH2C(CH3)2CHCl2CH2CH3CH2CH(CH3)CH2CF2BrCF2(CH3)2CHCH(CH3) CHF2CF2(C2H5)2CH CHFClCF2CH3(CH2)4CH2CF2BrCHF(CH3)2CH(CH2)2CH2CCl3CH2CH3(CH2)3CH(CH3) CBr3CH2(C2H5)2CHCH2FCH2CH2CH2CH3(CH2)5CH2ClCH2CH2CH2CH3(CH2)6CH2BrCH2CH2CH2CH3(CH2)5CH(CH3) ICH2CH2CH2TABLE 2CF3CH2CH2CHF2(CF2)3CH2CF3CF2CH2CH2＝CHCF3CHFCF2CH2＝CHCH2CH3CHClCH2CH3CH＝CHCH2CH2BrCHBrCH2CH2＝CHCH2CH2CHF2CF2CH2CH2＝CHCH(CH3)CH2ClCH(CH3) CH2＝C(CH3)CH2CH2BrCH(CH3) CH3CH2CH＝CHCH2(CH2F)2CH CH3CH＝CHCH(CH3)(CH2Cl)2CH CH3CH＝C(CH3)CH2(CH2Br)2CH (CH3)2C＝CHCH2(CF3)2CH CH2＝CHCH(C2H5)FCH2(CH2)2CH2CH2＝C(C2H5)CH2ClCH2(CH2)2CH2CH2＝CHCH2CH(CH3)BrCH2(CH2)2CH2CH2＝CHCH(CH3)CH2ICH2(CH2)2CH2CH2＝C(CH3)CH2CH2CH3CH(CH2Br)CH2CH3(CH2)2CH＝CHCH2CF3CHFCF2CH2CH3CH2CH＝CHCH2CH2CH2BrCH2CH(CH2Br) CH3CH＝CH(CH2)2CH2(CH3)2CClCH2CH2＝CH(CH2)3CH2FCH2(CH2)3CH2CH3CH2CH＝C(CH3)CH2ClCH2(CH2)3CH2(CH3)2C＝CHCH(CH3)BrCH2(CH2)3CH2CH2＝CH(CH2)2CH(CH3)ICH2(CH2)3CH2CH3CH＝CHCH(C2H5)CH2ClC(CH3)2CH2CH3CH＝C(C2H5)CH2CH2BrC(CH3)2CH2CH2＝CHCH(CH2CH2CH3)TABLE 3CH2＝C(CH(CH3)2)CH2CCl2＝CHCH2CH2CH3(CH2)3CH＝CHH2CBr2＝CCH2CH2(CH2＝CHCH2)2CH CCl2＝CH(CH2)3CH2CH3(CH2)3CH2CH(CH＝CH2) CH≡CCH2(CH3)2C＝CH(CH2)2- CH3C≡CCH2CH(CH3) CH≡CCH2CH2CH3(CH2)4CH＝CHCH2CH2CH≡CCH(CH3)CH3(CH2)5CH＝CHCH2CH2CH3CH2C≡CCH2(CH3)2C＝CH(CH2)2- CH3C≡CCH2CH2CH(CH3)CH2CH2CH≡C(CH2)2CH2CHCl＝CH2CH≡CCH2CH(CH3)CCl2＝CH2CH≡CCH(CH3)CH2CHCl＝CHCH2CH≡CCH(C2H5)CHBr＝CHCH2CH3(CH2)2C≡CCH2CH2＝CClCH2CH3CH2C≡CCH2CH2CF2＝CHCH2CH3(CH2)3C≡CCH2CHCl＝CClCH2CH3(CH2)3C≡CCH2CH2CHBr＝CBrCH2CH3(CH2)4CH(C≡CH)CH3CCl＝CHCH2CH3(CH2)4C≡CCH2CH2CH2ClCH＝CHCH2CH≡C(CH2)3CH2CF3CH＝CHCH2ClC≡CCH2CH2＝C(CH2Cl)CH2BrC≡CCH2CF3CCl＝CHCH2CH2ClC≡CCH2CF2BrCF＝CHCH2ClC≡CCH(CH3)CF3CF＝CHCH2BrC≡CCH(CH3)TABLE 4ClC ≡ CCH2CH2CH3CH2OCH2CH(CH3)BrC≡CCH2CH2CH3OCH(C2H5)CH2ClC≡C(CH2)2CH2CH3OCH2CH(C2H5)BrC≡C(CH2)2CH2CH3CH2O(CH2)2CH2ClC≡CCH(CH3)CH2CH3OCH(CH3)CH2CH2BrC≡CCH(CH3)CH2CH3OCH2CH(CH3)CH2ClC≡CCH2CH(CH3) CH3O(CH2)2CH(CH3)BrC≡CCH2CH(CH3) CH3(CH2)3OCH2CH2ClC≡CCH(C2H5) CH3OC(CH3)2CH2CH2BrC≡CCH(C2H5) CH3(CH2)3OCH2CH(CH3)CH3OCH2CH3SCH2CH3CH2OCH2CH3CH2SCH2CH3CH(OCH3) CH3CH(SCH3)CH3OCH2CH2CH3SCH2CH2CH3(CH2)2OCH2CH3(CH2)2SCH2(CH3)2CHOCH2(CH3)2CHSCH2CH3CH2OCH(CH3) CH3CH2SCH(CH3)CH3CH2OCH2CH2CH3CH2SCH2CH2CH3OCH(CH3)CH2CH3SCH(CH3)CH2CH3OCH2CH(CH3) CH3SCH2CH(CH3)CH3O(CH2)2CH2CH3S(CH2)2CH2CH3CH2CH(OCH3) CH3CH2CH(SCH3)CH3(CH2)2OCH2CH2CH3(CH2)2SCH2CH2(CH3)2CHOCH2CH2(CH3)2CHSCH2CH2CH3CH2OCH(CH3)CH2CH3CH2SCH(CH3)CH2TABLE 5CH3CH2SCH2CH(CH3) 2-isobutoxy cyclopentyl CH3SCH(C2H5)CH22-sec-butyloxy cyclopentyl CH3SCH2CH(C2H5) 2-tert-butyloxy cyclopentyl CH3CH2S(CH2)2CH2Cyclohexyl CH3SCH(CH3)CH2CH22-methylcyclohexyl CH3SCH2CH(CH3)CH23-methylcyclohexyl CH3S(CH2)2CH(H3) 4-methylcyclohexyl CH3S(CH2)3CH22-ethylcyclohexyl CH3SCH(CH3)CH(CH3) 4-Ethylcyclohexyl (CH)3)3CSCH2CH22, 3-dimethylcyclohexyl (CH)3)2CHCH2SCH2CH23, 4-dimethylcyclohexyl CH3CH2CH(CH3)SCH2CH23, 5-Dimethylcyclohexyl (CH)3)3CS(CH2)2CH23, 3, 5, 5-Tetramethylcyclohexyl (CH)3)2CHCH2S(CH2)2CH23-methoxycyclohexyl) CH3CH2CH(CH3)S(CH2)2CH23-ethoxycyclohexylcyclopropyl 3-n-propoxycyclocyclobutyl 3-isopropoxycyclohexylcyclopentyl 3-n-butoxycyclohexyl 2-methylcyclopentyl 3-isobutoxycyclohexyl 3-methylcyclopentyl 3-sec-butoxycyclohexyl 2-methoxycyclopentyl 3-tert-butoxycyclohexylButoxycyclohexyl 2-ethoxycyclopentyl 4-methoxycyclohexyl 2-n-propoxycyclopentyl 4-ethoxycyclohexyl 2-isopropoxycyclopentyl 4-n-propoxycyclohexyl 2-n-butoxycyclopentylTable 64-isopropoxycyclohexyl 3- (3, 3, 3, 2,
1-Hexafluoropropoxy) cyclopentyl 4-n-butyloxycyclohexyl 3- (trifluoromethoxy) cyclohexyl 4-isobutoxycyclohexyl 4- (trifluoromethoxy) cyclohexyl 4-sec-butyloxycyclohexyl 3- (difluoromethoxy) cyclohexyl 4-tert-butyloxycyclohexyl 4- (difluoromethoxy) cyclohexyl 3- (trifluoromethoxy) cyclopentyl 3- (bromodifluoromethoxy) cyclohexyl 3- (difluoromethoxy) cyclopentyl 4- (bromodifluoromethoxy) cyclohexyl 3- (bromodifluoromethoxy) cyclopentyl 3- (2, 2, 2-trifluoroethoxycyclopentyl 3- (2, 2, 2-trifluoroethoxycyclohexyl) cyclohexyl
Yl) cyclohexyl 3- (2, 2, 2-trifluoroethoxy) cyclopentyl 4- (2, 2, 2-trifluoroethoxy) cyclopentyl
Yl) cyclohexyl 3- (2, 2, 2, 1, 1-pentafluoroethoxy 3- (2, 2, 2, 1, 1-cyclopentylpentafluoroethoxy) cyclohexyl 3- (2-chloroethoxy) cyclopentyl 4- (2, 2, 2, 1, 1-
Pentafluoroethoxy) cyclohexyl 3- (2-bromoethoxy) cyclopentyl 3- (2-chloroethoxy) cyclohexyl 3- (2-chloro-1, 1, 2-trifluoroethoxy) 4- (2-chloroethoxy) cyclohexyl cyclopentyl 3- (2-bromo-1, 1, 2-trifluoroethoxy) cyclopentyl 3- (1, 1, 2, 2-tetrafluoroethoxy) cyclopentyl 3TABLE 73- (2-Bromoethoxy) cyclohexyl cyclopentylmethyl 3- (2-bromo)Ethoxy) cyclohexyl 2-cyclopentylethyl 3- (2-chloro-1, 1, 2-trifluoroethoxy) 3-cyclopentylpropylcyclohexyl 4- (2-chloro-1, 1, 2-trifluoroethoxy) cyclohexylmethylcyclohexyl 3- (2-bromo-1, 1, 2-trifluoroethoxy) 2-cyclohexylethylcyclohexyl 4- (2-bromo-1, 1, 2-trifluoroethoxy 3-cyclohexylpropylcyclohexyl 3- (1, 1, 2, 2-tetrafluoroethoxy) cyclo 2-cyclohexenylhexyl 4- (1, 1, 2, 2-tetrafluoroethoxy) cyclo 3-cyclohexenylhexyl 3- (3, 3, 3, 2, 2, 1-hexafluoropropoxy 3-methyl-2-cyclohexenyl) cyclohexyl 4- (33, 3, 2, 2, 1-hexafluoropropoxy 3, 5, 5-trimethyl-2-cyclyl) cyclohexylhexenylcyclopropylmethyl 2-cyclopentenyl (1-methylcyclopropyl) methyl 3-cyclopentenyl (2-methylcyclopropyl) methyl 3-methyl-2-cyclopentenyl 1-cyclopropylethyl (3-cyclohexenyl) methyl 2- (2-methylcyclopropyl) ethyl 2- (3-cyclohexenyl) ethylcyclobutylmethyl (1-cyclopentenyl) methylTABLE 8(R16)q(R15)q2-F 2，3，4，5，6-Cl53-F 2-Br4-F 3-Br2-Cl 4-Br3-Cl 3，5-Br24-Cl 2，4-Br22，3-Cl22-I2，6-Cl23-I3，5-Cl24-I2，4-Cl22-F，4-Cl3，4-Cl23-F，4-Cl2，5-Cl23-Cl，4-F2，3，4-Cl32-Br，4-F2，3，6-Cl32-F，4-Br2，4，6-Cl32-Br，5-F2，3，5-Cl32-Br，4-Cl2，4，5-Cl32-Cl，4-FTABLE-8-continuous 2-Cl, 4-Br 3-CH (CH)3)(CH2)2CH32-Cl，4-OCH33-CH(CH3)CH(CH3)23-CH3，4-Cl 3-CH(C2H5)22-CH3，4-F 3-C(CH3)2CH2CH33-CH3，4-F 3-(CH2)5CH32-Cl，4-CH33-(CH2)6CH32-Cl，5-CH33-(CH2)7CH32-CH3，4-Cl 4-CH33-C2H5，4-Cl 4-C2H52-Br，4-CH34-CH2CH2CH32-CH3，4-I 4-CH(CH3)22-Cl，5-CF34-(CH2)3CH32，4-Cl2，3-CH34-CH(CH3)CH2CH34-Cl，3，5-(CH3)24-CH2CH(CH3)24-Br，3，5-(CH3)24-C(CH3)34-Br，2，6-(CH3)24-(CH2)4CH34-Cl，4，5-(CH3)24-CH(CH3)(CH2)2CH32-CH(CH3)2，4-Cl，5-CH34-CH(CH3)CH(CHH3)23-CH34-CH(C2H5)23-C2H54-C(CH3)2CH2CH33-CH(CH3)24-(CH2)5CH33-C(CH3)34-(CH2)6CH33-CH2CH2CH2CH34-(CH2)7CH33-CH(CH3)CH2CH34-C(CH3)2CH2C(CH3)33-CH2CH2(CH3)22-Cl，4-C2H53-(CH2)4CH32-Cl，4-CH2CH2CH3TABLE-8 continuous 2-Cl, 4-CH (CH)3)24-CF32-Cl，4-(CH2)3CH33，5-(CF3)22-Cl，4-CH(H3)CH2CH32，4-(CF3)22-Cl，4-CH2CH(CH3)22-F，4-CF32-Br，4-CH2CH(CH3)22-Cl，4-CF32-Cl，4-C(CH3)32，6-Cl2，4-CF32-Cl，4-(CH2)4CH32-CF3，4-Cl2-Cl，4-CH(CH3)(CH2)2CH32，CF3，5-Cl2-Cl，4-CH(CH3)CH(CH3)22-Br，4-CF32-Cl，4-CH(C2H5)22-CF3，4-Br2-Cl，4-C(CH3)2CH2CH32-I，4-CF32-Br，4-C2H52-F，6-Cl，4-CF32-Br，4-(CH2)2CH32，6-F2，4-CF32-Br，4-CH(CH3)22-CCl32-Br，4-(CH2)3CH34-CCl32-Br，4-CH(CH3)CH2CH32-CHF22-Br，4-CH2CH(CH3)23-CHF22-Br，4-C(CH3)34-CHF22-Br，4-(CH2)4CH32-CF2Br2-Br，4-CH(CH3)(CH2)2CH33-CF2Br2-Br，4-CH(CH3)CH(CH3)24-CF2Br2-Br，4-CH(C2H5)23-CH2CF32-Br，4-C(CH3)2CH2CH34-CH2CF32-CF33-CH2CH2CF33-CF34-CH2CH2CF3TABLE-8 continuation of 3-CH2CF2CF34-OCH(CH3)(CH2)2CH34-CH2CF2CF34-OCH(CH3)CH(CH3)22-OCH34-OCH(C2H5)23-OCH33-OC(CH3)2CH2CH33-OC2H54-OC(CH3)2CH2CH33-OCH2CH2CH34-O(CH2)5CH33-OCH(CH3)24-O(CH2)6CH33-O(CH2)3CH33，5-{C(CH3)3}23-OCH(CH3)CH2CH33，5-(CH3)23-OCH2CH(CH3)23-CH3，5-CH(CH3)23-OC(CH3)33，4-(CH3)23-O(CH2)4CH32，4-(CH3)23-OCH(CH3)(CH2)(CH2)2CH32，5-(CH3)23-OCH(C2H5)22-CH(CH3)2，5-CH33-OCH(CH3)CH(CH3)23-CH3，4-CH(CH3)23-O(CH2)5CH33-CH3，5-CH(CH3)23-O(CH2)6CH32-C(CH3)3，5-CH34-OCH32-C(CH3)3，4-CH34-OC2H52，4-{C(CH3)3}24-OCH2CH2CH32，3，5-(CH3)34-OCH(CH3)23，4，5-(CH3)34-(CH2)3CH32，4，6-(CH3)34-OCH(CH3)CH2CH32，3-(OCH3)24-OCH2CH(CH3)23，5-(OCH3)24-OC(CH3)32-OCH3，4-CH34-O(CH2)4CH33，4-(OCH3)2TABLE-8 continuation 3-C2H5，4-OCH32-Br，4-OCH(CH3)(CH2)2CH33，4，5-(OCH3)32-Br，4-OCH(CH3)CH(CH3)23-Cl，5-OCH32-Br，4-OCH(C2H5)22-Cl，4-OC2H52-Br，4-OC(CH3)2CH2CH32-Cl，4-OCH2CH2CH33-OCH3，5-OC2H52-Cl，4-OCH(CH3)23，5-(OC2H5)22-Cl，4-O(CH2)3CH33，5-(OCH(CH3)2)22-Cl，4-OCH(CH3)CH2CH33-OCH3，5-OCH(CH3)22-Cl，4-OCH2CH(CH3)23-OC2H5，5-OCH(CH3)22-Cl，4-OC(CH3)22-CH3，3-OCH32-Cl，4-O(CH2)4CH32-CH3，3-OC2H52-Cl，4-OCH(CH3)(CH2)2CH33-CH3，3-OCH(CH3)22-Cl，4-OCH(CH3)CH(CH3)22-CH3，3-OCH(CH3)22-Cl，4-OCH2CH(C2H5)23-OCH3，4-Cl2-Cl，4-OC(CH3)2CH2CH33-OCH3，4-Br2-Br，4-OCH33-OC2H5，4-Cl2-Br，4-OC2H53-OC2H5，4-Br2-Br，4-O(CH2)2CH33-OCH(CH3)2，4-Cl2-Br，4-OCH(CH3)23-OCH(CH3)2，4-Br2-Br，4-O(CH2)3CH33-CH3，5-OCH32-Br，4-OCH(CH3)CH2CH33-CH3，5-OC2H52-Br，4-OCH2CH(CH3)23-CH3，5-OCH(CH3)22-Br，4-OC(CH3)32-CH3，4-OCH32-Br，4-O(CH2)4CH32-CH3，4-OC2H5TABLE-8 continuous 2-CH3，4-OCH(CH3)22-Cl，4-OCF32，3-(CH3)2，4-OCH32-Cl，4-OCHF22，3-(CH3)2，4-OC2H52-Cl，4-OCF2Br2，3-(CH3)2，4-OCH(CH3)22-Cl，4-OCH2CF32-OCF22-Cl，4-OCH2CH2CF33-OCF22-Cl，4-OCH2CF2CF34-OCF22-Cl，4-OCF2CF2H2-OCHF22-Cl，4-OCF2CFHCl3-OCHF22-Cl，4-OCF2CFHBr4-OCHF23-OCF2CF32-OCF2Br 4-OCF2CF33-OCF2Br 2-SCH34-OCF2Br 3-SCH33-OCH2CF34-SCH34-OCH2CF32-CH3，4-SCH33-OCF2CFHCl 2-CH3，4-SCH34-OCF2CFHCl 2-SC2H53-OCF2CFHBr 3-SC2H54-OCF2CFHBr 3-SCH2CH2CH33-OCF2CF2H 3-SCH(CH3)24-OCF2CF2H 4-SC2H53-OCH2CH2CF34-S(CH2)2CH34-OCH2CH2CF34-SCH(CH3)23-OCH2CF2CF32-SCF34-OCH2CF2CF33-SCF3TABLE-8 continuous 4-SCF34-OCH2CH＝CHCH33-SCHF23-OCH2CH＝C(CH3)24-SCHF24-OCH2CH＝C(CH3)23-SCF2Br 3-OCH2C(CH3)＝CHCH34-SCF2Br 4-OCH2C(CH3)＝CHCH33-SCH2CF33-OCH2C＝CHC2H54-SCH2CF34-OCH2CH＝CHC2H53-SCF2CFHCl 3-OCH2CH＝CH(CH2)2CH34-SCF2CFHCl 4-OCH2CH＝CH(CH2)2CH33-SCF2CFHBr 3-OCH2CH＝CCl24-SCF2CFHBr 4-OCH2CH＝CCl23-SCF2CF2H 3-OCH2CH＝CBr24-SCF2CF2H 4-OCH2CH＝CBr23-SCH2CF2CF33-OCH2C(Cl)＝CH(Cl)4-SCH2CF2CF34-OCH2C(Cl)＝CH(Cl)3-SCH2CH2CF34-OCH2C(Br)＝CH(Br)4-SCH2CH2CF34-OCH2C(Br)＝CH(Br)3-SCF2CF33-OCH2C(Cl)＝CH24-SCF2CF34-OCH2C(Cl)＝CH23-CH3，4-SCH33-OCH2CH＝CH(Cl)3-OCH2CH＝CH24-OCH2CH＝CH(Cl)4-OCH2CH＝CH23-OCH2C(Br)＝CH23-OCH(CH3)CH＝CH24-OCH2C(Br)＝CH24-OCH(CH3)CH＝CH23-OCH2CH＝CClCH33-OCH2CH＝CHCH34-OCH2CH＝CClCH3TABLE 8-continuous 3-cyclopentyl 3-phenoxy 4-cyclopentyl 4-phenoxy 3-cyclohexyl 2-Cl, 4-cyclopentyl 4-cyclohexyl 2-Cl, 4-cyclohexyl 3-phenyl 2-Cl, 4-phenyl 2-Cl, 4-cyclohexyl 3-O-cyclopentyl 2-Cl, 4-O-cyclopentyl 2-Cl, 4-O-cyclohexyl 3-O-cyclohexyl 2-Cl, 4-phenoxy 4-O-cyclohexyl 2-Cl
Figure A9711002500511
TABLE 9 (R)16)q(R16)qH 3-OCH2C ≡ CBr 2-F3-cyclopentyl 2-Cl 3-cyclohexyl 3-F3- (3-cyclopentenyl) 3-Cl 3- (2-cyclopentenyl) 3-CH33- (3-cyclohexenyl) 3-CF33- (2-cyclohexenyl) 3-OCH33-Cyclopropoxy 3-OCF33-Cyclobutoxy 3-SCH33-cyclopentyloxy 3-SC2H53-Cyclohexyloxy 3-SCF2CHF23- (3-cyclopentenyl) oxy 3-OCH2CH＝CH23- (2-cyclopentenyl) oxy 3-OCH2CH＝CCl23- (3-cyclohexenyl) oxy 3-OCH2CH＝CBr23- (2-cyclohexenyl) oxy 3-OCH2C≡CH 3-OC6H53-OCH2C≡CCl 3-(o-CH3C6H4O)TABLE-9 continuation of 3- (m-CH)3C6H4O) 3-(p-FC6H4CH2O)3-(p-CH3C6H4O) 3-(o-BrC6H4CH2O)3-(o-ClC6H4O) 3-(m-BrC6H4CH2O)3-(m-ClC6H4O) 3-(p-BrC6H4CH2O)3-(p-ClC6H4O) 3-(o-CH3C6H4CH2O)3-(o-FC6H4O) 3-(m-CH3C6H4CH2O)3-(m-FC6H4O) 3-(p-CH3C6H4CH2O)3-(p-FC6H4O) 3-(o-CF3C6H4CH2O)3-(o-CF3C6H4O) 3-(m-CF3C6H4CH2O)3-(m-CF3C6H4O) 3-(p-CF3C6H4CH2O)3-(p-CF3C6H4O) 3-CH2C6H53-(m-(CH3)3CC6H4O) 4-F3-(p-(CH3)3CC6H4O) 4-Cl3-(m-CH3OC6H4O) 4-CH33-(p-CH3OC6H4O) 4-OCH33-(3，4-Cl2C6H3O) 4-CF33-(3，5-Cl2C6H3O) 4-OCF33-(m-CF3OC6H4O) 4-SCH33-(p-CF3OC6H4O) 4-OCH2CH＝CH23-C6H54-OCH2CH＝CCl23-CH2C6H54-OCH2CH＝CBr23-(o-ClC6H4CH2O) 4-CH＝CH23-(m-ClC6H4CH2O) 4-OCH2C≡CH3-(p-ClC6H4CH2O) 4-OCH2C≡CCl3-(o-FC6H4CH2O) 4-OCH2C≡CBr3-(m-FC6H4CH2O) 4-cyclopentylTABLE 9-CONTINUOUS 4-CYCLOHEXYL 4- (p-CH)3C6H4O)4- (3-cyclopentenyl) 4- (O-CF3C6H4O)4- (2-cyclopentenyl) 4- (m-CF3C6H4O)4- (3-cyclohexenyl) 4- (p-CF3C6H4O)4- (2-Cyclohexenyl) 4- (m- (CH)3)3CC6H4O) 4-Cyclopropoxy 4- (p- (CH)3)3CC6H4O) 4-Cyclobutoxy 4- (m-CH)3OC6H4O) 4-cyclopentyloxy 4- (p-CH3OC6H4O) 4-Cyclohexyloxy 4- (mCF)3OC6H4O)4- (3-cyclopentenyl) oxy 4- (p-CF3OC6H4O)4- (2-cyclopentenyl) oxy 4-CH2C6H54- (3-cyclohexenyl) oxy 4-OCH2C6H54- (1-cyclohexenyl) oxy 4- (o-ClC)6H4CH2O)4- (2-cyclohexenyl) 4- (m-ClC6H4CH2O)4-C6H54-(p-ClC6H4CH2O)4-OC6H54-(o-FC6H4CH2O)4-(o-ClC6H4O) 4-(m-FC6H4CH2O)4-(m-ClC6H4O) 4-(P-FC6H4CH2O)4-(p-ClC6H4O) 4-(o-BrC6H4CH2O)4-(o-FC6H4O) 4-(m-BrC6H4CH2O)4-(m-FC6H6O) 4-(p-BrC6H4CH2O)4-(p-FC6H4O) 4-(o-CH3C6H4CH2O)4-(o-CH3C6H4O) 4-(m-CH3C6H4CH2O)4-(m-CH3C6H4O) 4-(P-CH3C6H4CH2O)TABLE 9 continuous 4- (o-CF)3C6H4CH2O) 4-Br，3-OCH2C6H54-(m-CF3C6H4CH2O) 4-CH3，3-OC6H54-(p-CF3C6H4CH2O) 4-CH3，3-OCH2C6H54-(m-CF3OC6H4CH2O) 3-F，4-OC6H54-(p-CF3OC4H4CH2O) 3-F，4-OCH2C6H52-F，5-(p-FC6H4O) 3-Cl，4-OC6H54-F，3-OC6H53-Cl，4-OCH2C6H54-F，3-OCH2C6H53-Br，4-OCH2C6H54-Cl，3-OC6H53-CH3，4-OC6H54-Cl，3-OCH2C6H53-CH3，4-OCH2C6H5Watch 10(R16)q(R16)qH 3-OCH2C ≡ CBr 2-F3-cyclopentyl 2-Cl 3-cyclohexyl 3-F3- (3-cyclopentenyl) 3-Cl 3- (2-cyclopentenyl) 3-CH33- (3-cyclohexenyl) 3-CF33- (2-cyclohexenyl) 3-OCH33-Cyclopropoxy 3-OCF33-Cyclobutoxy 3-SCH33-cyclopentyloxy 3-SC2H53-Cyclohexyloxy 3-SCF2CHF23- (3-cyclopentenyl) oxy 3-OCH2CH＝CH23- (2-cyclopentenyl) oxy 3-OCH2CH＝CCl23- (3-cyclohexenyl) oxy 3-OCH2CH＝CBr23- (2-cyclohexenyl) oxy 3-OCH2C≡CH 3-OC6H53-OCH2C≡CCl 3-(o-CH3C6H4O)TABLE 10-continuous 3- (m-CH)3C6H4O) 3-(p-FC6H4CH2O)3-(p-CH3C6H4O) 3-(o-BrC6H4CH2O)3-(o-ClC6H4O) 3-(m-BrC6H4CH2O)3-(m-ClC6H4O) 3-(p-BrC6H4CH2O)3-(p-ClC6H4O)3-(o-CH3C6H4CH2O)3-(o-FC6H4O) 3-(m-CH3C6H4CH2O)3-(m-FC6H4O) 3-(p-CH3C6H4CH2O)3-(p-FC6H4O) 3-(o-CF3C6H4CH2O)3-(o-CF3C6H4O) 3-(m-CF3C6H4CH2O)3-(m-CF3C6H4O) 3-(p-CF3C6H4CH2O)3-(p-CF3C6H4O) 3-CH2C6H53-(m-(CH3)3CC6H4O) 4-F3-(p-(CH3)3CC6H4O) 4-Cl3-(m-CH3OC6H4O) 4-CH33-(p-CH3OC6H4O) 4-OCH33-(3，4-Cl2C6H3O) 4-CF33-(3，5-Cl2C6H3O) 4-OCF33-(m-CF3OC6H4O) 4-SCH33-(p-CF3OC6H4O) 4-OCH2CH＝CH23-C6H54-OCH2CH＝CCl23-CH2C6H54-OCH2CH＝CBr23-(o-ClC6H4CH2O) 4-CH＝CH23-(m-ClC6H4CH2O) 4-OCH2C≡CH3-(p-ClC6H4CH2O) 4-OCH2C≡CCl3-(o-FC6H4CH2O) 4-OCH2C≡CBr3-(m-FC6H4CH2O) 4-cyclopentylTABLE 10-CONTINUOUS 4-CYCLOHEXYL 4- (p-CH)3C6H4O)4- (3-cyclopentenyl) 4- (O-CF3C6H4O)4- (2-cyclopentenyl) 4-(m-CF3C6H4O)4- (3-cyclohexenyl) 4- (p-CF3C6H4O)4- (2-Cyclohexenyl) 4- (m- (CH)3)3CC6H4O) 4-Cyclopropoxy 4- (p- (CH)3)3CC6H4O) 4-Cyclobutoxy 4- (m-CH)3OC6H4O) 4-cyclopentyloxy 4- (p-CH3OC6H4O) 4-Cyclohexyloxy 4- (m-CF)3OC6H4O)4- (3-cyclopentenyl) oxy 4- (p-CF3OC6H4O)4- (2-cyclopentenyl) oxy 4-CH2C6H54- (3-cyclohexenyl) oxy 4-OCH2C6H54- (1-cyclohexenyl) oxy 4- (o-ClC)6H4CH2O)4- (2-cyclohexenyl) oxy 4- (m-ClC6H4CH2O)4-C6H54-(p-ClC6H4CH2O)4-OC6H54-(o-FC6H4CH2O)4-(o-ClC6H4O) 4-(m-FC6H4CH2O)4-(m-ClC6H4O) 4-(P-FC6H5CH2O)4-(p-ClC6H4O) 4-(o-BrC6H4CH2O)4-(o-FC6H4O) 4-(m-BrC6H4CH2O)4-(m-FC6H4O) 4-(p-BrC6H4CH2O)4-(p-FC6H4O) 4-(o-CH3C6H4CH2O)4-(o-CH3C6H4O) 4-(m-CH3C6H4CH2O)4-(m-CH3C6H4O) 4-(P-CH3C6H4CH2O)TABLE 10 continuous 4- (o-CF)3C6H4CH2O) 4-CH3，3-OC6H54-(m-CF3C6H4CH2O)4-CH3，3-OCH2C6H54-(p-CF3C6H4CH2O) 3-F，4-OC6H54-(m-CF3OC6H4CH2O) 3-F，4-OCH2C6H54-(p-CF3OC6H4CH2O) 3-Cl，4-OC6H52-F，5-(p-FC6H4O) 3-Cl，4-OCH2C6H54-F，3-OC6H53-Br，4-OCH2C6H54-F，3-OCH2C6H53-CH3，4-OC6H54-Cl，3-OC6H53-CH3，4-OCH2C6H5-Cl，3-OCH2C6H54-Br，3-OCH2C6H5TABLE 11(R16)q(R16)qH 3-(p-CF3C6H4O) 3-F3-cyclopentyl 3-Cl 3-cyclohexyl 3-Br 3-cyclopentyloxy 3-CH33-Cyclohexyloxy 3-OCH33-OCH2CH＝CCl23-CF33-OCH2CH＝CBr23-OCF34-F3-CN 4-Cl3-NO24-Br3-OC6H54-CH33-CH2C6H54-OCH33-OCH2C6H54-CF33-(p-FC6H4O) 4-OCF33-(p-ClC6H4O) 4-CN3-(p-CH3C6H4O) 4-NO23-(m-CF3C6H4O) 4-OC6H5TABLE 11-CONTINUOUS 4-CH2C6H54-Cl，3-OC6H54-OCH2C6H54-Cl，3-OCH2C6H54-(p-FC6H4O) 4-CH3，3-OC6H54-(p-ClC6H4O) 4-CH3，3-OC6H4CH24-(p-CH3C6H4O) 4-Br，3-OC2HC6H54-(m-CF3C6H4O) 3-F，4-OC6H54-(p-CF3C6H4O) 3-F，4-OCH2C6H54-cyclopentyl 3-Cl, 4-OC6H54-cyclohexyl-3-Cl, 4-OCH2C6H54-cyclopentyloxy 3-CH3，4-OC6H54-Cyclohexyloxy 3-CH3，4-OCH2C6H54-OCH2CH＝CCl23-Br，4-OCH2C6H54-OCH2CH＝CBr23-Cl，4-OCH2CH＝CCl24-F，3-OC6H53-Cl，4-OCH2CH＝CBr24-F，3-OCH2C6H5TABLE 12
Figure A9711002500611
(R16)q(R16)qH 3-(p-CF3C6H4O) 3-F3-cyclopentyl 3-Cl 3-cyclohexyl 3-Br 3-cyclopentyloxy 3-CH33-Cyclohexyloxy 3-OCH33-OCH2CH＝CCl23-CF33-OCH2CH＝CBr23-OCF34-F3-CN 4-Cl3-NO24-Br3-OC6H54-CH33-CH2C6H54-OCH33-OCH2C6H54-CF33-(p-FC6H4O) 4-OCF33-(p-ClC6H4O) 4-CN3-(p-CH3C6H4O) 4-NO23-(m-CF3C6H4O) 4-OC6H5TABLE 12-CONTINUOUS 4-CH2C6H54-Cl，3-OC6H54-OCH2C6H54-Cl，3-OCH2C6H54-(p-FC6H4O) 4-CH3，3-OC6H54-(p-ClC6H4O) 4-CH3，3-OC6H4CH24-(p-CH3C6H4O) 4-Br，3-OCH2C6H54-(m-CF3C6H4O) 3-F，4-OC6H54-(p-CF3C6H4O) 3-F，4-OCH2C6H54-cyclopentyl 3-Cl, 4-OC6H54-cyclohexyl-3-Cl, 4-OCH2C6H54-cyclopentyloxy 3-CH3，4-OC6H54-Cyclohexyloxy 3-CH3，4-OCH2C6H54-OCH2CH＝CCl23-Br，4-OCH2C6H54-OCH2CH＝CBr23-Cl，4-OCH2CH＝CCl24-F，3-OC6H53-Cl，4-OCH2CH＝CBr24-F，3-OCH2C6H5Watch 13
Figure A9711002500631
(R16)qR5R6R7H H H H2-F H H H2-Cl H H H2-CH3H H H2-CF3H H H2-CH3O H H H 3-F H H H3-Cl H H H3-Br H H H3-CH3H H H3-CF3H H H3-OCH3H H H3-OC2H5H H H3-O(CH2)2CH3H H H3-OCH(CH3)2H H H3-OCF3H H H3-OCHF2H H HTABLE 13-CONTINUO 3-OCF2Br H H H3-OCH2CF3H H H3-OCF2CHF2H H H3-OCF2CHFCF3H H H4-F H H H4-Cl H H H4-Br H H H 4-CH3H H H4-CF3H H H4-OCH3H H H 4-OC2H5H H H4-O(CH2)2CH3H H H4-OCH(CH3)2H H H 4-OCF3H H H4-OCHF2H H H4-OCF2Br H H H4-OCH2CF3H H H4-OCF2CHF2H H H4-OCF2CHFCF3H H H2，4-F2H H H2，5-F2H H H2，6-F2H H H3，4-F2H H H3，5-F2H H H3，5-(OCH3)2H H H3，4-OCH2O H H HTABLE 13-CONTINUO 3-OCH3，4-OCH2H5H H H3-F，4-OCH(CH3)2H H H3-Cl，4-OCH(CH3)2H H H4-CN H H H4-NO2H H H2，3-F2H H HH H H CH3H H H C2H5H H H -CH2CH2CH3HH H -CH(CH3)2H CH3H HH CH(CH3)2H H4-F CH(CH3)2H H4-Cl CH(CH3)2H HH CF3H H4-F CF3H H4-Cl CF3H HTABLE 14(R16)qR5R6R7(R16)qR5R6R7H H H H 4-OCF3H H H4-F H H H 4-CN H H H4-Cl H H H 4-NO2H H H4-Br H H H H CH3H H4-CH3H H H H CH(CH3)2H H4-CF3H H H H CF3H H4-OCH3H H H H H H CH3Watch 15(R16)qR5R6R7(R16)qR5R6R7H CH3H H H CH3CH3H table 16R5R6R7i (R16)qH H H 2 HH H H 3 HH H H 2 4-ClH H H 3 4-ClTABLE 16-continuous H H24-FH H34-FH H24-BrH H34-BrH H24-CH3H H H 3 4-CH3H H H 2 4-CF3H H H 3 4-CF3H H H 2 4-OCH3H H H 3 4-OCH3H H H 2 4-OCF3HH H 3 4-OCF3H H H 2 4-CO2CH3H H H 3 4-CO2CH3H H H 2 4-SCH3H H H 3 4-SCH3H H H 2 4-SCF3H H H 3 4-SCF3H H H 2 4-NHCOCH3H H H 3 4-NHCOCH3H H H 2 4-CONHCH3H H H 3 4-CONHCH3H H H 2 3-ClH H H 3 3-ClH H H 2 3-FH H H 3 3-FTABLE 16-continuous H H H 2 3-BrH H H 3 3-BrH H H 2 3-CH3H H H 3 3-CH3H H H 2 3-CF3H H H 3 3-CF3H H H 2 3-OCH3H H H 3 3-OCH3H H H 2 3-OCF3H H H 3 3-OCF3H H H 2 3-SCH3H H H 3 3-SCH3H H H 2 3-SCF3H H H 3 3-SCF3H H H 2 3-CONHCH3H H H 3 3-CONHCH3H H H 2 2-ClH H H 3 2-ClTABLE 17B R5R6R7i (R16)qO H H H 0 HO H H H 1 HO H H H 2 HO H H H 3 HO H H H 4 HO H H H 0 4-FO H H H 1 4-FO H H H 2 4-FO H H H 3 4-FO H H H 4 4-FO H H H 0 4-ClO H H H 1 4-ClO H H H 2 4-ClO H H H 3 4-ClO H H H 4 4-ClO H H H 0 4-BrO H H H 1 4-BrTABLE 17-continuous O H H H24-BrO H H H34-BrO H H H 4 4-BrO H H H 0 4-CNO H H H 1 4-CNO H H H 2 4-CNO H H H 3 4-CNO H H H 4 4-CNO H H H 0 4-NO2O H H H 1 4-NO2O H H H 2 4-NO2O H H H 3 4-NO2O H H H 4 4-NO2O H H H 0 4-CO2CH3O H H H 1 4-CO2CH3O H H H 2 4-CO2CH3O H H H 3 4-CO2CH3O H H H 4 4-CO2CH3O H H H 0 4-CH3O H H H 1 4-CH3O H H H 2 4-CH3O H H H 3 4-CH3O H H H 4 4-CH3O H H H 0 4-CF3O H H H 1 4-CF3O H H H 2 4-CF3TABLE 17-continuous O H H H34-CF3O H H H 4 4-CF3O H H H 0 4-OCH3O H H H 1 4-OCH3O H H H 2 4-OCH3O H H H 3 4-OCH3O H H H 4 4-OCH3O H H H 0 4-OC2H5O H H H 1 4-OC2H5O H H H 2 4-OC2H5O H H H 3 4-OC2H5O H H H 4 4-OC2H5O H H H 0 4-O(CH2)2CH3O H H H 1 4-O(CH2)2CH3O H H H 2 4-O(CH2)2CH3O H H H 3 4-O(CH2)2CH3O H H H 4 4-O(CH2)2CH3O H H H 0 4-OCH(CH3)2O H H H 1 4-OCH(CH3)2O H H H 2 4-OCH(CH3)2O H H H 3 4-OCH(CH3)2O H H H 4 4-OCH(CH3)2O H H H 0 4-OCF3O H H H 1 4-OCF3O H H H 2 4-OCF3TABLE 17 continuous O H H H34-OCF3O H H H 4 4-OCF3O H H H 0 4-OCF2CHF2O H H H 1 4-OCF2CHF2O H H H 2 4-OCF2CHF2O H H H 3 4-OCF2CHF2O H H H 4 4-OCF2CHF2O H H H 0 4-SCH3O H H H 1 4-SCH3O H H H 2 4-SCH3O H H H 3 4-SCH3O H H H 4 4-SCH3O H H H 0 4-SCF3O H H H 1 4-SCF3O H H H 2 4-SCF3O H H H 3 4-SCF3O H H H 4 4-SCF3O H H H 0 4-CH3S(O)O H H H 1 4-CH3S(O)O H H H 2 4-CH3S(O)O H H H 3 4-CH3S(O)O H H H 4 4-CH3S(O)O H H H 0 4-CH3S(O)2O H H H 1 4-CH3S(O)2O H H H 2 4-CH3S(O)2TABLE 17-continuous OHH H34-CH3S(O)2O H H H 4 4-CH3S(O)2O H H H 0 4-CF3S(O)O H H H 1 4-CF3S(O)O H H H 2 4-CF3S(O)O H H H 3 4-CF3S(O)O H H H 4 4-CF3S(O)O H H H 0 4-CF3S(O)2O H H H 1 4-CF3S(O)2O H H H 2 4-CF3S(O)2O H H H 3 4-CF3S(O)2O H H H 4 4-CF3S(O)2O H H H 0 4-OCH2CH＝CCl2O H H H 1 4-OCH2CH＝CCl2O H H H 2 4-OCH2CH＝CCl2O H H H 3 4-OCH2CH＝CCl2O H H H 4 4-OCH2CH＝CCl2O H H H 0 4-OCH2CH＝CBr2O H H H 1 4-OCH2CH＝CBrO H H H 2 4-OCH2CH＝CBr2O H H H 3 4-OCH2CH＝CBr2O H H H 4 4-OCH2CH＝CBr2O H H H 0 4-CH2OCH3O H H H 1 4-CH2OCH3O H H H 2 4-CH2OCH3TABLE 17-continuous OHH H34-CH2OCH3O H H H 4 4-CH2OCH3O H H H 0 4-CH2SCH3O H H H 1 4-CH2SCH3O H H H 2 4-CH2SCH3O H H H 3 4-CH2SCH3O H H H 4 4-CH2SCH3O H H H 0 4-N(CH3)2O H H H 1 4-N(CH3)2O H H H 2 4-N(CH3)2O H H H 3 4-N(CH3)2O H H H 4 4-N(CH3)2O H H H 0 4-NHCOCH3O H H H 1 4-NHCOCH3O H H H 2 4-NHCOCH3O H H H 3 4-NHCOCH3O H H H 4 4-NHCOCH3O H H H 0 4-CHOO H H H 1 4-CHOO H H H 2 4-CHOO H H H 3 4-CHOO H H H 4 4-CHOO H H H 0 4-CONHCH3O H H H 1 4-CONHCH3O H H H 2 4-CONHCH3O H H H 3 4-CONHCH3TABLE 17 continuous O H H H44-CONHCH3O H H H 0 4-CON(CH3)2O H H H 1 4-CON(CH3)2O H H H 2 4-CON(CH3)2O H H H 3 4-CON(CH3)2O H H H 4 4-CON(CH3)2O H H04-Cyclopentyloxy O H H14-Cyclopentyloxy O H H24-Cyclopentyloxy O H H H34-Cyclopentyloxy O H H44-Cyclopentyloxy O H H04-Cyclohexyloxy O H H14-Cyclohexyloxy O H H H24-Cyclohexyloxy O H H34-Cyclohexyloxy O H H44-Cyclohexyloxy O H H04-C6H5O H H H 1 4-C6H5O H H H 2 4-C6H5O H H H 3 4-C6H5O H H H 4 4-C6H5O H H H 0 4-C6H5OO H H H 1 4-C6H5OO H H H 2 4-C6H5OO H H H 3 4-C6H5OTABLE 17-continuous O H H44-C6H5OO H H H 0 4-C6H5CH2O H H H 1 4-C6H5CH2O H H H 2 4-C6H5CH2O H H H 3 4-C6H5CH2O H H H 4 4-C6H5CH2O H H H 0 4-C6H5CH2CO H H H 1 4-C6H5CH2CO H H H 2 4-C6H5CH2CO H H H 3 4-C6H5CH2CO H H H 4 4-C6H5CH2CO H H H 0 4-(4-FC6H4O)O H H H 1 4-(4-FC6H4O)O H H H 2 4-(4-FC6H4O)O H H H 3 4-(4-FC6H4O)O H H H 4 4-(4-FC6H4O)O HH H 0 4-(4-ClC6H4O)O H H H 1 4-(4-ClC6H4O)O H H H 2 4-(4-ClC6H4O)O H H H 3 4-(4-ClC6H4O)O H H H 4 4-(4-ClC6H4O)O H H H 0 4-(4-CH3C6H4O)O H H H 1 4-(4-CH3C6H4O)O H H H 2 4-(4-CH3C6H4O)O H H H 3 4-(4-CH3C6H4O)TABLE 17-continuous O H H44- (4-CH)3C6H4O)O H H H 0 4-(3-CF3C6H4O)O H H H 1 4-(3-CF3C6H4O)O H H H 2 4-(3-CF3C6H4O)O H H H 3 4-(3-CF3C6H4O)O H H H 4 4-(3-CF3C6H4O)O H H H 0 4-(4-CF3C6H4O)O H H H 1 4-(4-CF3C6H4O)O H H H 2 4-(4-CF3C6H4O)O H H H 3 4-(4-CF3C6H4O)O H H H 4 4-(4-CF3C6H4O)O H H H 0 3-FO H H H 1 3-FO H H H 2 3-FO H H H 3 3-FO H H H 4 3-FO H H H 0 3-ClO H H H 1 3-ClO H H H 2 3-ClO H H H 3 3-ClO H H H 4 3-ClO H H H 0 3-BrO H H H 1 3-BrO H H H 2 3-BrO H H H 3 3-BrTABLE 17-continuous O H H H43-BrO H H03-CNO H H13-CNO H H H23-CNO H H33-CNO H H H43-CNO H H03-NO2O H H H 1 3-NO2O H H H 2 3-NO2O H H H 3 3-NO2O H H H 4 3-NO2O H H H 0 3-CH3O H H H 1 3-CH3O H H H 2 3-CH3O H H H 3 3-CH3O H H H 4 3-CH3O H H H 0 3-CF3O H H H 1 3-CF3O H H H 2 3-CF3O H H H 3 3-CF3O H H H 4 3-CF3O H H H 0 3-OCH3O H H H 1 3-OCH3O H H H 2 3-OCH3O H H H 3 3-OCH3O H H H 4 3-OCH3TABLE 17 continuous O H H H03-OC2H5O H H H 1 3-OC2H5O H H H 2 3-OC2H5O H H H 3 3-OC2H5O H H H 4 3-OC2H5O H H H 0 3-O(CHH2)2CH3O H H H 1 3-O(CH2)2CH3O H H H 2 3-O(CH2)2CH3O H H H 3 3-O(CH2)2CH3O H H H 4 3-O(CH2)2CH3O H H H 0 3-OCH(CH3)2O H H H 1 3-OCH(CH3)2O H H H 2 3-OCH(CH3)2O H H H 3 3-OCH(CH3)2O H H H 4 3-OCH(CH3)2O H H H 0 3-OCF3O H H H 1 3-OCF3O H H H 2 3-OCF3O H H H 3 3-OCF3O H H H 4 3-OCF3O H H H 0 3-SCH3O H H H 1 3-SCH3O H H H 2 3-SCH3O H H H 3 3-SCH3O H H H 4 3-SCH3TABLE 17 continuous O H H H03-SCF3O H H H 1 3-SCF3O H H H 2 3-SCF3O H H H 3 3-SCF3O H H H 4 3-SCF3O H H H 0 3-CONHCH3O H H H 1 3-CONHCH3O H H H 2 3-CONHCH3O H H H 3 3-CONHCH3O H H H 4 3-CONHCH3O H H H 0 3-CON(CH3)2O H H H 1 3-CON(CH3)2O H H H 2 3-CON(CH3)2O H H H 3 3-CON(CH3)2O H H H 4 3-CON(CH3)2O H H03-Cyclopentyloxy O H H13-Cyclopentyloxy O H H23-Cyclopentyloxy O H H H33-Cyclopentyloxy O H H43-Cyclopentyloxy O H H H03-cyclohexyloxy O H H13-cyclohexyloxy O H H H23-cyclohexyloxy O H H33-cyclohexyloxy O H H H43-cyclohexyloxyTABLE 17-continuous O H H H03-C6H5O H H H 1 3-C6H5O H H H 2 3-C6H5O H H H 3 3-C6H5O H H H 4 3-C6H5O H H H 0 3-C6H5OO H H H 1 3-C6H5OO H H H 2 3-C6H5OO H H H 3 3-C6H5OO H H H 4 3-C6H5OO H H H 0 3-C6H5CH2O H H H 1 3-C6H5CH2O H H H 2 3-C6H5CH2O H H H 3 3-C6H5CH2O H H H 4 3-C6H5CH2O H H H 0 3-C6H5CH2OO H H H 1 3-C6H5CH2OO H H H 2 3-C6H5CH2OO H H H 3 3-C6H5CH2OO H H H 4 3-C6H5CH2OO H H H 0 3-(4-FC6H4O)O H H H 1 3-(4-FC6H4O)O H H H 2 3-(4-FC6H4O)O H H H 3 3-(4-FC6H4O)O H H H 4 3-(4-FC6H4O)TABLE 17 continuous O H H03- (4-ClC)6H4O)O H H H 1 3-(4-ClC6H4O)O H H H 2 3-(4-ClC6H4O)O H H H 3 3-(4-ClC6H4O)O H H H 4 3-(4-ClC6H4O)O H H H 0 3-(4-CH3C6H4O)O H H H 1 3-(4-CH3C6H4O)O H H H 2 3-(4-CH3C6H4O)O H H H 3 3-(4-CH3C6H4O)O H H H 4 3-(4-CH3C6H4O)O H H H 0 3-(3-CF3C6H4O)O H H H 1 3-(3-CF3C6H4O)O H H H 2 3-(3-CF3C6H4O)O H H H 3 3-(3-CF3C6H4O)O H H H 4 3-(3-CF3C6H4O)O H H H 0 3-(4-CF3C6H4O)O H H H 1 3-(4-CF3C6H4O)O H H H 2 3-(4-CF3C6H4O)O H H H 3 3-(4-CF3C6H4O)O H H H 4 3-(4-CF3C6H4O)O H H H 0 2-FO H H H 1 2-FO H H H 2 2-FO H H H 3 2-FO H H H 4 2-FO H H H 0 2-ClTABLE 17-continuous O H H H12-ClO H H22-ClO H H32-ClO H H42-ClO H H02-BrO H H12-BrO H H22-BrO H H32-BrO H H42-BrO H H02-CH3O H H H 1 2-CH3O H H H 2 2-CH3O H H H 3 2-CH3O H H H 4 2-CH3O H H H 0 2-CF3O H H H 1 2-CF3O H H H 2 2-CF3O H H H 3 2-CF3O H H H 4 2-CF3O H H H 0 2-OCH3O H H H 1 2-OCH3O H H H 2 2-OCH3O H H H 3 2-OCH3O H H H 4 2-OCH3O H H H 0 2-OCF3TABLE 17 continuous O H H H12-OCF3O H H H 2 2-OCF3O H H H 3 2-OCF3O H H H 4 2-OCF3O H H H 0 2-CONHCH3O H H H 1 2-CONHCH3O H H H 2 2-CONHCH3O H H H 3 2-CONHCH3O H H H 4 2-CONHCH3O H H H 0 2-CON(CH3)2O H H H 1 2-CON(CH3)2O H H H 2 2-CON(CH3)2O H H H 3 2-CON(CH3)2O H H H 4 2-CON(CH3)2O H H H 0 2-C6H5O H H H 1 2-C6H5O H H H 2 2-C6H5O H H H 3 2-C6H5O H H H 4 2-C6H5O H H H 0 2-SCH3O H H H 1 2-SCH3O H H H 2 2-SCH3O H H H 3 2-SCH3O H H H 4 2-SCH3O H H H 0 2-SCF3TABLE 17 continuous O H H H12-SCF3O HH H 2 2-SCF3O H H H 3 2-SCF3O H H H 4 2-SCF3S H H H 0 4-FS H H H 1 4-FS H H H 2 4-FS H H H 3 4-FS H H H 4 4-FS H H H 0 4-ClS H H H 1 4-ClS H H H 2 4-ClS H H H 3 4-ClS H H H 4 4-ClS H H H 0 4-BrS H H H 1 4-BrS H H H 2 4-BrS H H H 3 4-BrS H H H 4 4-BrS H H H 0 4-CH3S H H H 1 4-CH3S H H H 2 4-CH3S H H H 3 4-CH3S H H H 4 4-CH3S H H H 0 4-CF3TABLE 17-continuous S H H H14-CF3S H H H 2 4-CF3S H H H 3 4-CF3S H H H 4 4-CF3S H H H 0 4-OCH3S H H H 1 4-OCH3S H H H 2 4-OCH3S H H H 3 4-OCH3S H H H 4 4-OCH3S H H H 0 4-OCF3S H H H 1 4-OCF3S H H H 2 4-OCF3S H H H 3 4-OCF3S H H H 4 4-OCF3S H H H 0 4-SCH3S H H H 1 4-SCH3S H H H 2 4-SCH3S H H H 3 4-SCH3S H H H 4 4-SCH3S H H H 0 4-SCF3S H H H 1 4-SCF3S H H H 2 4-SCF3S H H H 3 4-SCF3S H H H 4 4-SCF3S H H04-Cyclopentyloxy S H H14-CyclopentyloxyTABLE 17-Serpentos HH 24-cyclopentyloxy S H H34-cyclopentyloxy S H H44-cyclopentyloxy S H04-cyclohexyloxy S H H14-cyclohexyloxy S H H24-cyclohexyloxy S HH34-cyclohexyloxy S H H44-cyclohexyloxy S H H04-C6H5S H H H 1 4-C6H5S H H H 2 4-C6H5S H H H 3 4-C6H5S H H H 4 4-C6H5S H H H 0 4-C6H5OS H H H 1 4-C6H5OS H H H 2 4-C6H5OS H H H 3 4-C6H5OS H H H 4 4-C6H5OS H H H 0 4-C6H5CH2S H H H 1 4-C6H5CH2S H H H 2 4-C6H5CH2S H H H 3 4-C6H5CH2S H H H 4 4-C6H5CH2S H H H 0 4-C6H5CH2OS H H H 1 4-C6H5CH2OTABLE 17-CONTINUOUS SH H24-C6H5CH2OS H H H 3 4-C6H5CH2OS H H H 4 4-C6H5CH2OS H H H 0 3-FS H H H 1 3-FS H H H 2 3-FS H H H 3 3-FS H H H 4 3-FS H H H 0 3-ClS H H H 1 3-ClS H H H 2 3-ClS H H H 3 3-ClS H H H 4 3-ClS H H H 0 3-BrS H H H 1 3-BrS H H H 2 3-BrS H H H 3 3-BrS H H H 4 3-BrS H H H 0 3-CH3S H H H 1 3-CH3S H H H 2 3-CH3S H H H 3 3-CH3S H H H 4 3-CH3S H H H 0 3-CF3S H H H 1 3-CF3TABLE 17-continuous S H H H23-CF3S HH H 3 3-CF3S H H H 4 3-CF3S H H H 0 3-OCH3S H H H 1 3-OCH3S H H H 2 3-OCH3S H H H 3 3-OCH3S H H H 4 3-OCH3S H H H 0 3-OCF3S H H H 1 3-OCF3S H H H 2 3-OCF3S H H H 3 3-OCF3S H H H 4 3-OCF3S H H H 0 3-SCH3S H H H 1 3-SCH3S H H H 2 3-SCH3S H H H 3 3-SCH3S H H H 4 3-SCH3S H H H 0 3-SCF3S H H H 1 3-SCF3S H H H 2 3-SCF3S H H H 3 3-SCF3S H H H 4 3-SCF3S H H03-Cyclopentyloxy S H H13-CyclopentyloxyTABLE 17-Sereno NaH 23-cyclopentyloxy-NaH 33-cyclopentyloxy-NaH 43-Cyclopentyloxy S H03-cyclohexyloxy S H H13-cyclohexyloxy S H H23-cyclohexyloxy S H H H33-cyclohexyloxy S H H43-cyclohexyloxy S H H H03-C6H5S H H H 1 3-C6H5S H H H 2 3-C6H5S H H H 3 3-C6H5S H H H 4 3-C6H5S H H H 0 3-C6H5OS H H H 1 3-C6H5OS H H H 2 3-C6H5OS H H H 3 3-C6H5OS H H H 4 3-C6H5OS H H H 0 3-C6H5CH2S H H H 1 3-C6H5CH2S H H H 2 3-C6H5CH2S H H H 3 3-C6H5CH2S H H H 4 3-C6H5CH2S H H H 03-C6H5CH2OS H H H 1 3-C6H5CH2OS H H H 2 3-C6H5CH2OTABLE 17-CONTINUOUS SH H33-C6H5CH2OS H H H 4 3-C6H5CH2ONH H H H 0 HNH H H H 1 HNH H H H 2 HNH H H H 3 HNH H H H 4 HNH H H H 0 4-FNH H H H 1 4-FNH H H H 2 4-FNH H H H 3 4-FNH H H H 4 4-FNH H H H 0 4-BrNH H H H 1 4-BrNH H H H 2 4-BrNH H H H 3 4-BrNH H H H 4 4-BrNH H H H 0 4-CH3NH H H H 1 4-CH3NH H H H 2 4-CH3NH H H H 3 4-CH3NH H H H 4 4-CH3NH H H H 0 4-CF3NH H H H 1 4-CF3NH H H H 2 4-CF3TABLE 17-continuous NH H H H34-CF3NH H H H 4 4-CF3NH H H H 0 4-OCH3NH H H H 1 4-OCH3NH H H H 2 4-OCH3NH H H H 3 4-OCH3NH H H H 4 4-OCH3NH H H H 0 4-OCF3NH H H H 1 4-OCF3NH H H H 2 4-OCF3NH H H H 3 4-OCF3NH H H H 4 4-OCF3NH H H H 0 4-SCH3NH H H H 1 4-SCH3NH H H H 2 4-SCH3NH H H H 3 4-SCH3NH H H H 4 4-SCH3NH H H H 0 4-SCF3NH H H H 1 4-SCF3NH H H H 2 4-SCF3NH H H H 3 4-SCF3NH H HH 4 4-SCF3NH H H H 0 4-CONHCH3NH H H H 1 4-CONHCH3NH H H H 2 4-CONHCH3TABLE 17-continuous NH H H34-CONHCH3NH H H H 4 4-CONHCH3NH H H H 0 4-CON(CH3)2NH H H H 1 4-CON(CH3)2NH H H H 2 4-CON(CH3)2NH H H H 3 4-CON(CH3)2NH H H H 4 4-CON(CH3)2NH H H H 0 3-FNH H H H 1 3-FNH H H H 2 3-FNH H H H 3 3-FNH H H H 4 3-FNH H H H 0 3-ClNH H H H 1 3-ClNH H H H 2 3-ClNH H H H 3 3-ClNH H H H 4 3-ClNH H H H 0 3-BrNH H H H 1 3-BrNH H H H 2 3-BrNH H H H 3 3-BrNH H H H 4 3-BrNH H H H 0 3-CH3NH H H H 1 3-CH3NH H H H 2 3-CH3TABLE 17-NH H H33-CH3NH H H H 4 3-CH3NH H H H 0 3-CF3NH H H H 1 3-CF3NH H H H 2 3-CF3NH H H H 3 3-CF3NH H H H 4 3-CF3NH H H H 0 3-CH3ONH H H H 1 3-CH3ONH H H H 2 3-CH3ONH H H H 3 3-CH3ONH H H H 4 3-CH3ONH H H H 0 3-CF3ONH H H H 1 3-CF3ONH H H H 2 3-CF3ONH H H H 3 3-CF3ONH H H H 4 3-CF3ONH H H H 0 3-CH3SNH H H H 1 3-CH3SNH H H H 2 3-CH3SNH H H H 3 3-CH3SNH H H H 4 3-CH3SNH H H H 0 3-CF3SNH H H H 1 3-CF3SNH H H H 2 3-CF3SNH H H H 3 3-CF3STABLE 17-continuous NH H H H43-CF3SNH H H H 0 3-CONHCH3NH H H H 1 3-CONHCH3NH H H H 2 3-CONHCH3NH H H H 3 3-CONHCH3NH H H H 4 3-CONHCH3NH H H H 0 3-CON(CH3)2NH H H H 1 3-CON(CH3)2NH H H H 2 3-CON(CH3)2NH H H H 3 3-CON(CH3)2NH H H H 4 3-CON(CH3)2NCH3H H H 0 3-CF3NCH3H H H 1 3-CF3NCH3H H H 2 3-CF3NCH3H H H 3 3-CF3NCH3H H H 4 3-CF3NCH3H H H 0 HNCH3H H H 1 HNCH3H H H 2 HNCH3H H H 3 HNCH3H H H 4 HNCH3H H H 0 4-FNCH3H H H 1 4-FNCH3H H H 2 4-FNCH3H H H 3 4-FTABLE 17 continuous NCH3H H H 4 4-FNCH3H H H 0 4-ClNCH3H H H 1 4-ClNCH3H H H 2 4-ClNCH3H H H 3 4-ClNCH3H H H 4 4-ClNCH3H H H 0 4-BrNCH3H H H 1 4-BrNCH3H H H 2 4-BrNCH3H H H 3 4-BrNCH3H H H 4 4-BrNCH3H H H 0 4-CH3NCH3H H H 1 4-CH3NCH3H H H 2 4-CH3NCH3H H H 3 4-CH3NCH3H H H 4 4-CH3NCH3H H H 0 4-CF3NCH3H H H 1 4-CF3NCH3H H H 2 4-CF3NCH3H H H 3 4-CF3NCH3H H H 4 4-CF3NCH3H H H 0 3-FNCH3H H H 1 3-FNCH3H H H 2 3-FNCH3H H H 3 3-FTABLE 17 continuous NCH3H H H 4 3-FNCH3H H H 0 3-ClNCH3H H H 1 3-ClNCH3H H H 2 3-ClNCH3H H H 3 3-ClNCH3H H H 4 3-ClNCH3H H H 0 3-BrNCH3H H H 1 3-BrNCH3H H H 2 3-BrNCH3H H H 3 3-BrNCH3H H H 4 3-BrNCH3H H H 0 3-CH3NCH3H H H 1 3-CH3NCH3H H H 2 3-CH3NCH3H H H 3 3-CH3NCH3H H H 4 3-CH3C(＝O)O H H H 0 HC(＝O)O H H H 1 HC(＝O)O H H H 2 HC(＝O)O H H H 3 HC(＝O)O H H H 4 HC(＝O)O H H H 0 4-FC(＝O)O H H H 1 4-FC(＝O)O H H H 2 4-FC(＝O)O H H H 3 4-FTable 17 — C (═ O) ohhh 44 — FC (═ O) ohh 04 — ClC (═ O) ohhh 14 — ClC (═ O) ohhh 24 — ClC (═ O) ohhh 34 — ClC (═ O) ohhh 44 — ClC (═ O) ohh 04 — BrC (═ O) ohhh 14 — BrC (═ O) ohh 24 — BrC (═ O) ohhh 34 — BrC (═ O) ohh 44 — BrC (═ O) ohh 04 — CH H44 —BrC (═ O) ohh 04 — CH ═ O) ohh 243C(＝O)O H H H 1 4-CH3C(＝O)O H H H 2 4-CH3C(＝O)O H H H 3 4-CH3C(＝O)O H H H 4 4-CH3C(＝O)O H H H O 4-CF3C(＝O)O H H H 1 4-CF3C(＝O)O H H H 2 4-CF3C(＝O)O H H H 3 4-CF3C(＝O)O H H H 4 4-CF3C(＝O)O H H H 0 4-OCH3C(＝O)O H H H 1 4-OCH3C(＝O)O H H H 2 4-OCH3C(＝O)O H H H 3 4-OCH3C(＝O)O H H H 4 4-OCH3Table 17-continuous C (═ O) oh H04-OCF3C(＝O)O H H H 1 4-OCF3C(＝O)O H H H 2 4-OCF3C(＝O)O H H H 3 4-OCF3C(＝O)O H H H 4 4-OCF3C(＝O)O H H H 0 4-CONHCH3C(＝O)O H H H 1 4-CONHCH3C(＝O)O H H H 2 4-CONHCH3C(＝O)O H H H 3 4-CONHCH3C(＝O)O H H H 4 4-CONHCH3C(＝O)O H H H 0 4-CON(CH3)2C(＝O)O H H H 1 4-CON(CH3)2C(＝O)O H H H 2 4-CON(CH3)2C(＝O)O H H H 3 4-CON(CH3)2C(＝O)O H H H 4 4-CON(CH3)2C(＝O)O H H H 0 3-FC(＝O)O H H H 1 3-FC(＝O)O H H H 2 3-FC(＝O)O H H H 3 3-FC(＝O)O H H H 4 3-FC(＝O)O H H H 0 3-ClC(＝O)O H H H 1 3-ClC(＝O)O H H H 2 3-ClC(＝O)O H H H 3 3-ClC(＝O)O H H H 4 3-ClTABLE 17 continuationC(＝O)O H H H 0 3-BrC(＝O)O H H H 13-BrC(＝O)O H H H 2 3-BrC(＝O)O H H H 3 3-BrC(＝O)O H H H 4 3-BrC(＝O)O H H H 0 3-CH3C(＝O)O H H H 1 3-CH3C(＝O)O H H H 2 3-CH3C(＝O)O H H H 3 3-CH3C(＝O)O H H H 4 3-CH3C(＝O)O H H H 0 3-CF3C(＝O)O H H H 1 3-CF3C(＝O)O H H H 2 3-CF3C(＝O)O H H H 3 3-CF3C(＝O)O H H H 4 3-CF3C(＝O)O H H H 0 3-OCH3C(＝O)O H H H 1 3-OCH3C(＝O)O H H H 2 3-OCH3C(＝O)O H H H 3 3-OCH3C(＝O)O H H H 4 3-OCH3C(＝O)O H H H 0 3-OCF3C(＝O)O H H H 1 3-OCF3C(＝O)O H H H 2 3-OCF3C(＝O)O H H H 3 3-OCF3C(＝O)O H H H 4 3-OCF3Table 17-continuous C (═ O) ohh H03-CONHCH3C(＝O)O H H H 1 3-CONHCH3C(＝O)O H H H 2 3-CONHCH3C(＝O)O H H H 3 3-CONHCH3C(＝O)O H H H 4 3-CONHCH3C(＝O)O H H H 0 3-CON(CH3)2C(＝O)O H H H 1 3-CON(CH3)2C(＝O)O H H H 2 3-CON(CH3)2C(＝O)O H H H 3 3-CON(CH3)2C(＝O)O H H H 4 3-CON(CH3)2C(＝O)NH H H H 0 HC(＝O)NH H H H 1 HC(＝O)NH H H H 2 HC(＝O)NH H H H 3 HC(＝O)NH H H H 4 HC(＝O)NH H H H 0 4-FC(＝O)NH H H H 1 4-FC(＝O)NH H H H 2 4-FC(＝O)NH H H H 3 4-FC(＝O)NH H H H 4 4-FC(＝O)NHH H H 0 4-ClC(＝O)NH H H H 1 4-ClC(＝O)NH H H H 2 4-ClC(＝O)NH H H H 3 4-ClC(＝O)NH H H H 4 4-ClTable 17-C (═ O) NH H04-BrC (═ O) NH H14-BrC (═ O) NH H24-BrC (═ O) NH H34-BrC (═ O) NH H44-BrC (═ O) NH H04-CH3C(＝O)NH H H H 1 4-CH3C(＝O)NH H H H 2 4-CH3C(＝O)NH H H H 3 4-CH3C(＝O)NH H H H 4 4-CH3C(＝O)NH H H H 0 4-CF3C(＝O)NH H H H 1 4-CF3C(＝O)NH H H H 2 4-CF3C(＝O)NH H H H 3 4-CF3C(＝O)NH H H H 4 4-CF3C(＝O)NH H H H 0 4-OCH3C(＝O)NH H H H 1 4-OCH3C(＝O)NH H H H 2 4-OCH3C(＝O)NH H H H 3 4-OCH3C(＝O)NH H H H 4 4-OCH3C(＝O)NH H H H 0 4-OCF3C(＝O)NH H H H 1 4-OCF3C(＝O)NH H H H 2 4-OCF3C(＝O)NH H H H 3 4-OCF3C(＝O)NH H H H 4 4-OCF3C(＝O)NH H H H 0 4-CONHCH3Table 17-continuous C (═ O) NH H14-CONHCH3C(＝O)NH H H H 2 4-CONHCH3C(＝O)NH H H H 3 4-CONHCH3C(＝O)NH H H H 4 4-CONHCH3C(＝O)NH H H H 0 4-CON(CH3)2C(＝O)NH H H H 1 4-CON(CH3)2C(＝O)NH H H H 2 4-CON(CH3)2C(＝O)NH H H H 3 4-CON(CH3)2C(＝O)NH H H H 4 4-CON(CH3)2C(＝O)NH H H H 0 3-FC(＝O)NH H H H 1 3-FC(＝O)NH H H H 2 3-FC(＝O)NH H H H 3 3-FC(＝O)NH HH H 4 3-FC(＝O)NH H H H 0 3-ClC(＝O)NH H H H 1 3-ClC(＝O)NH H H H 2 3-ClC(＝O)NH H H H 3 3-ClC(＝O)NH H H H 4 3-ClC(＝O)NH H H H 0 3-BrC(＝O)NH H H H 1 3-BrC(＝O)NH H H H 2 3-BrC(＝O)NH H H H 3 3-BrC(＝O)NH H H H 4 3-BrC(＝O)NH H H H 0 3-CH3Table 17-C (═ O) NH H13 — CH3C(＝O)NH H H H 2 3-CH3C(＝O)NH H H H 3 3-CH3C(＝O)NH H H H 4 3-CH3C(＝O)NH H H H O 3-CF3C(＝O)NH H H H 1 3-CF3C(＝O)NH H H H 2 3-CF3C(＝O)NH H H H 3 3-CF3C(＝O)NH H H H 4 3-CF3C(＝O)NH H H H 0 3-OCH3C(＝O)NH H H H 1 3-OCH3C(＝O)NH H H H 2 3-OCH3C(＝O)NH H H H 3 3-OCH3C(＝O)NH H H H 4 3-OCH3C(＝O)NH H H H 0 3-OCF3C(＝O)NH H H H 1 3-OCF3C(＝O)NH H H H 2 3-OCF3C(＝O)NH H H H 3 3-OCF3C(＝O)NH H H H 4 3-OCF3C(＝O)NH H H H 0 3-CONHCH3C(＝O)NH H H H 1 3-CONHCH3C(＝O)NH H H H 2 3-CONHCH3C(＝O)NH H H H 3 3-CONHCH3C(＝O)NH H H H 4 3-CONHCH3C(＝O)NH H H H 0 3-CON(CH3)2Table 17-C (═ O) NH H13-CON (CH)3)2C(＝O)NH H H H 2 3-CON(CH3)2C(＝O)NH H H H 3 3-CON(CH3)2C(＝O)NH H H H 4 3-CON(CH3)2OC(＝O) H H H 0 HOC(＝O) H H H1 HOC(＝O) H H H 2 HOC(＝O) H H H 3 HOC(＝O) H H H 4 HOC(＝O) H H H 0 4-FOC(＝O) H H H 1 4-FOC(＝O) H H H 2 4-FOC(＝O) H H H 3 4-FOC(＝O) H H H 4 4-FOC(＝O) H H H 0 4-ClOC(＝O) H H H 1 4-ClOC(＝O) H H H 2 4-ClOC(＝O) H H H 3 4-ClOC(＝O) H H H 4 4-ClOC(＝O) H H H 0 4-BrOC(＝O) H H H 1 4-BrOC(＝O) H H H 2 4-BrOC(＝O) H H H 3 4-BrOC(＝O) H H H 4 4-BrOC(＝O) H H H 0 4-CH3Table 17-continuous OC (═ O) hh 14-CH3OC(＝O) H H H 2 4-CH3OC(＝O) H H H 3 4-CH3OC(＝O) H H H 4 4-CH3OC(＝O) H H H 0 4-CF3OC(＝O) H H H 1 4-CF3OC(＝O) H H H 2 4-CF3OC(＝O) H H H 3 4-CF3OC(＝O) H H H 4 4-CF3OC(＝O) H H H 0 3-FOC(＝O) H H H 1 3-FOC(＝O) H H H 2 3-FOC(＝O) H H H 3 3-FOC(＝O) H H H 4 3-FOC(＝O) H H H 0 3-ClOC(＝O) H H H 1 3-Cl OC(＝O) H H H 2 3-ClOC(＝O) H H H 3 3-ClOC(＝O) H H H 4 3-ClOC(＝O) H H H 0 3-BrOC(＝O) H H H 1 3-BrOC(＝O) H H H 2 3-BrOC(＝O) H H H 3 3-BrOC(＝O) H H H 4 3-BrOC(＝O) H H H 0 3-CH3OC(＝O) H H H 1 3-CH3TABLE 17-OC (═ O) H H H23-CH3OC(＝O) H H H 3 3-CH3OC(＝O) H H H 4 3-CH3OC(＝O) H H H 0 3-CF3OC(＝O) H H H 1 3-CF3OC(＝O) H H H 2 3-CF3OC(＝O) H H H 3 3-CF3OC(＝O) H H H 4 3-CF3OC(＝O) H H H 0 2-ClOC(＝O) H H H 1 2-ClOC(＝O) H H H 2 2-ClOC(＝O) H H H 3 2-ClOC(＝O) H H H 4 2-ClNHC(＝O) H H H 0 HNHC(＝O) H H H 1 HNHC(＝O) H H H 2 HNHC(＝O) H H H 3 HNHC(＝O) H H H 4 HNHC(＝O) H H H 0 4-FNHC(＝O) H H H 1 4-FNHC(＝O) H H H 2 4-FNHC(＝O) H H H 3 4-FNHC(＝O) H H H 4 4-FNHC(＝O) H H H 0 4-ClNHC(＝O) H H H 1 4-ClTable 17-continuous NHC (═ O) hh 24-ClNHC (═ O) hh 34-ClNHC (═ O) hh 44-ClNHC (═ O) hh 04-BrNHC (═ O) hh 14-BrNHC (═ O) hh 24-BrNHC (═ O) hh 34-BrNHC (═ O) hh 44-BrNHC (═ O) hh 04-CH H04-CH3NHC(＝O) H H H 1 4-CH3NHC(＝O) H H H 2 4-CH3NHC(＝O) H H H 3 4-CH3NHC(＝O) H H H 4 4-CH3NHC(＝O) H H H 0 4-OCH3NHC(＝O) H H H 1 4-OCH3NHC(＝O) H H H 2 4-OCH3NHC(＝O) H H H 3 4-OCH3NHC(＝O) H H H 4 4-OCH3NHC(＝O) H H H 0 4-CF3NHC(＝O) H H H 1 4-CF3NHC(＝O) H H H 2 4-CF3NHC(＝O) H H H 3 4-CF3NHC(＝O) H H H 4 4-CF3NHC(＝O) H H H 0 4-OCF3NHC(＝O) H H H 1 4-OCF3TABLE 17-CONTINNHC (═ O) H H24-OCF3NHC(＝O) H H H 3 4-OCF3NHC(＝O) H H H 4 4-OCF3NHC(＝O) H H H 0 3-FNHC(＝O) H H H 1 3-FNHC(＝O) H HH 2 3-FNHC(＝O) H H H 3 3-FNHC(＝O) H H H 4 3-FNHC(＝O) H H H 0 3-ClNHC(＝O) H H H 1 3-ClNHC(＝O) H H H 2 3-ClNHC(＝O) H H H 3 3-ClNHC(＝O) H H H 4 3-ClNHC(＝O) H H H 0 3-BrNHC(＝O) H H H 1 3-BrNHC(＝O) H H H 2 3-BrNHC(＝O) H H H 3 3-BrNHC(＝O) H H H 4 3-BrNHC(＝O) H H H 0 3-CH3NHC(＝O) H H H 1 3-CH3NHC(＝O) H H H 2 3-CH3NHC(＝O) H H H 3 3-CH3NHC(＝O) H H H 4 3-CH3NHC(＝O) H H H 0 3-OCH3NHC(＝O) H H H 1 3-OCH3TABLE 17-CONTINNHC (═ O) H H23-OCH3NHC(＝O) H H H 3 3-OCH3NHC(＝O) H H H 4 3-OCH3NHC(＝O) H H H 0 3-CF3NHC(＝O) H H H 1 3-CF3NHC(＝O) H H H 2 3-CF3NHC(＝O) H H H 3 3-CF3NHC(＝O) H H H 4 3-CF3NHC(＝O) H H H 0 3-OCF3NHC(＝O) H H H 1 3-OCF3NHC(＝O) H H H 2 3-OCF3NHC(＝O) H H H 3 3-OCF3NHC(＝O) H H H 4 3-OCF3C(＝O)N(CH3) H H H 0 HC(＝O)N(CH3) H H H 1 HC(＝O)N(CH3) H H H 2 HC(＝O)N(CH3) H H H 3 HC(＝O)N(CH3) H H H 4 HC(＝O)N(CH3) H H H 0 4-ClC(＝O)N(CH3) H H H 1 4-ClC(＝O)N(CH3) H H H 2 4-ClC(＝O)N(CH3) H H H 3 4-ClC(＝O)N(CH3) H H H 4 4-ClC(＝O)N(CH3) H H H0 4-CF3C(＝O)N(CH3) H H H 1 4-CF3C(＝O)N(CH3) H H H 2 4-CF3TABLE 17 continuation C(＝O)N(CH3) H H H 3 4-CF3C(＝O)N(CH3) H H H 4 4-CF3Watch 18(R16)q(R16)q6-CH33，6-(CH3)26-CH2CH33，5-(CH3)26-CH2CH2CH34，5-(CH3)26-phenyl 4, 6- (CH)3)25-CH35，6-(CH3)25-CH2CH36-Cl5-CH(CH3)25-Cl5-C(CH3)34-Cl 5-phenyl 3-Cl4-CH36-Br4-CH2CH35-Br4-CH(CH3)24-Br4-C(CH3)33-Br 4-phenyl 5-CF35-CH36-phenyl-4-CF3TABLE 18 continuation 3-CF33，4，5，6-F43，5-Cl23，5-Cl2，4，6-F23，5-(CF3)23，4，5，6-Cl43，6-(CF3)26-Cl，3，5-(CH3)24，5-(CF3)26-OCH34，6-(CF3)26-OC2H53-Cl，5-CF36-OCH(CH3)23-Br，5-CF35-OCH35-Cl，3-CF35-OC2H56-Cl，3-CF35-OCH(CH3)26-Cl，4-CF34-OCH36-Cl，5-CF34-OC2H53，5，6-F34-OCH(CH3)23，5，6-F3，4-CH3Watch 19B R5R6R7i (R16)qO H H H 0 HO H H H 1 HO H H H 2 HO H H H 3 HO H H H 4 HO H H H 5 HO H H H 6 HNH H H H 0 HNH H H H 1 HNH H H H 2 HNH H H H 3 HNH H H H 4 HS H H H 0 HS H H H 1 HS H H H 2 HS H H H 3 HTABLE 19-ONLY NH H H H5 HNH H H6 HS H H4 HS H H5 HS H H6 HO H H05-ClO H H15-ClO H H25-ClO H H35-ClO H H45-ClO H H55-ClO H H65-ClNH H H05-ClNH H15-ClNH H H25-ClNH H H H35-ClNH H45-ClNH H H H H 5 5-ClNH H H H 6 5-ClS H H H 0 5-ClS H H H 1 5-ClS H H H 2 5-ClS H H H 3 5-ClS H H H 4 5-ClS H H H 5 5-ClS H H H 6 5-ClTABLE 19-continuous N-CH3H H H 0 5-ClN-CH3H H H 1 5-ClN-CH3H H H 2 5-ClN-CH3H H H 3 5-CLN-CH3H H H 4 5-CLN-CH3H H H 5 5-CLN-CH3H H H 6 5-CLNH H H H 0 5-CH3NH H H H 1 5-CH3NH H H H 2 5-CH3NH H H H 3 5-CH3NH H H H 4 5-CH3NH H H H 5 5-CH3NH H H H 6 5-CH3O H H H 0 5-CH3O H H H 1 5-CH3O H H H 2 5-CH3O H H H 3 5-CH3O H H H 4 5-CH3O H H H 5 5-CH3O HH H 6 5-CH3S H H H 0 5-CH3S H H H 1 5-CH3S H H H 2 5-CH3S H H H 3 5-CH3TABLE 19-CONTINUOUS SH H45-CH3S H H H 5 5-CH3S H H H 6 5-CH3NH H H H 0 5-BrNH H H H 1 5-BrNH H H H 2 5-BrNH H H H 3 5-BrNH H H H 4 5-BrNH H H H 5 5-BrNH H H H 6 5-BrO H H H 0 5-BrO H H H 1 5-BrO H H H 2 5-BrO H H H 3 5-BrO H H H 4 5-BrO H H H 5 5-BrO H H H 6 5-BrS H H H 0 5-BrS H H H 1 5-BrS H H H 2 5-BrS H H H 3 5-BrS H H H 4 5-BrS H H H 5 5-BrS H H H 6 5-BrNH H H H 0 3-Cl，5-CF3TABLE 19-NH H H13-Cl, 5-CF3NH H H H 2 3-Cl，5-CF3NH H H H 3 3-Cl，5-CF3NH H H H 4 3-Cl，5-CF3NH H H H 5 3-Cl，5-CF3NH H H H 6 3-Cl，5-CF3O H H H 0 3-Cl，5-CF3O H H H 1 3-Cl，5-CF3O H H H 2 3-Cl，5-CF3O H H H 3 3-Cl，5-CF3O H H H 4 3-Cl，5-CF3O H H H 5 3-Cl，5-CF3O H H H 6 3-Cl，5-CF3S H H H 0 3-Cl，5-CF3S H H H 1 3-Cl，5-CF3S H H H 2 3-Cl，5-CF3S H H H 3 3-Cl，5-CF3S H H H 4 3-Cl，5-CF3S H H H 5 3-Cl，5-CF3S H H H 6 3-Cl，5-CF3O H HH 0 5-NO2O H H H 1 5-NO2O H H H 2 5-NO2O H H H 3 5-NO2O H H H 4 5-NO2TABLE 19-continuous O H H H55-NO2O H H H 6 5-NO2O H H H 0 3-NO2，5-BrO H H H 1 3-NO2，5-BrO H H H 2 3-NO2，5-BrO H H H 3 3-NO2，5-BrO H H H 4 3-NO2，5-BrO H H H 5 3-NO2，5-BrO H H H 6 3-NO2，5-BrO H H H 0 3-NO2，4-CHO H H H 1 3-NO2，4-CHO H H H 2 3-NO2，4-CH3O H H H 3 3-NO2，4-CH3O H H H 4 3-NO2，4-CH3O H H H 5 3-NO2，4-CH3O H H H 6 3-NO2，4-CH3O H H H 0 4-CH3，5-NO2O H H H 1 4-CH3，5-NO2O H H H 2 4-CH3，5-NO2O H H H 3 4-CH3，5-NO2O H H H 4 4-CH3，5-NO2O H H H 5 4-CH3，5-NO2O H H H 6 4-CH3，5-NO2O H H H 0 5-CF3O H H H 1 5-CF3O H H H 2 5-CF3TABLE 19-continuous OHH H35-CF3O H H H 4 5-CF3O H H H 5 5-CF3O H H H 6 5-CF3S H H H 0 5-CF3S H H H 1 5-CF3S H H H 2 5-CF3S H H H 3 5-CF3S H H H 4 5-CF3S H H H 5 5-CF3S H H H 6 5-CF3NH H H H 0 5-CF3NH H H H 1 5-CF3NH H H H 2 5-CF3NH H H H 3 5-CF3NH H H H 4 5-CF3NH H H H 5 5-CF3NH H H H 6 5-CF3N(CH3) H H H 0 5-CF3N(CH3) H H H 1 5-CF3N(CH3) H H H 2 5-CF3N(CH3) H H H 3 5-CF3N(CH3) H H H 4 5-CF3N(CH3) H H H 5 5-CF3N(CH3) H H H 6 5-CF3Table 19 — C (═ O) O H0 HC (═ O) O H1 HC (═ O) O H2 HC (═ O) O H3 HC (═ O) O H4 HC (═ O) O H5 HC (═ O) O H6 HC (═ O) NH H0 HC (═ O) NH H1 HC (═ O) NH H2 HC (═ O) NH H3 HC (═ O) NH H4 HC (═ O) NH H5 HC (═ O) NH H6 HNHC (═ O) H0 HNHC (═ O) H1 HNHC (═ O) H2 HNHC (═ O) H3 HC (═ O) H4 HC (═ O) H2 HNHC (═ O) H3 HC (═ O) H4 HC O) hh H5 HNHC (═ O) hh H6 HNHC (═ O) hh 05-CF3NHC(＝O) H H H 1 5-CF3NHC(＝O) H H H 2 5-CF3NHC(＝O) H H H 3 5-CF3NHC(＝O) H H H 4 5-CF3TABLE 19-CONTINUONHC (═ O) H H55-CF3NHC(＝O) H H H 6 5-CF3C(＝O)O H H H 0 5-CF3C(＝O)O H H H 1 5-CF3C(＝O)O H H H 2 5-CF3C(＝O)O H H H 3 5-CF3C(＝O)O H H H 4 5-CF3C(＝O)O H H H 5 5-CF3C(＝O)O H H H 6 5-CF3C(＝O)NH H H H 0 5-CF3C(＝O)NH H H H 1 5-CF3C(＝O)NH H H H 2 5-CF3C(＝O)NH HH H 3 5-CF3C(＝O)NH H H H 4 5-CF3C(＝O)NH H H H 5 5-CF3C(＝O)NH H H H 6 5-CF3N(CH3) H H H 0 HN(CH3) H H H 1 HN(CH3) H H H 2 HN(CH3) H H H 3 HN(CH3) H H H 4 HN(CH3) H H H 5 HN(CH3) H H H 6 HOC(＝O) H H H 0 HOC(＝O) H H H 1 HTable 19-continuous OC (═ O) H2 HOC (═ O)H H H 3 HOC(＝O) H H H 4 HOC(＝O) H H H 5 HOC(＝O) H H H 6 HC(＝O)O H H H 0 5-ClC(＝O)O H H H 1 5-ClC(＝O)O H H H 2 5-ClC(＝O)O H H H 3 5-ClC(＝O)O H H H 4 5-ClC(＝O)O H H H 5 5-ClC(＝O)O H H H 6 5-ClC(＝O)NH H H H 0 5-ClC(＝O)NH H H H 1 5-ClC(＝O)NH H H H 2 5-ClC(＝O)NH H H H 3 5-ClC(＝O)NH H H H 4 5-ClC(＝O)NH H H H 5 5-ClC(＝O)NH H H H 6 5-ClNHC(＝O) H H H 0 5-ClNHC(＝O) H H H 1 5-ClNHC(＝O) H H H 2 5-ClNHC(＝O) H H H 3 5-ClNHC(＝O) H H H 4 5-ClNHC(＝O) H H H 5 5-ClNHC(＝O) H H H 6 5-ClTABLE 19-continuous N (CH)3) H H H 0 5-CH3N(CH3) H H H l 5-CH3N(CH3) H H H 2 5-CH3N(CH3) H H H 3 5-CH3N(CH3) H H H 4 5-CH3N(CH3) H H H 5 5-CH3N(CH3) H H H 6 5-CH3C(＝O)O H H H 0 5-CH3C(＝O)O H H H 1 5-CH3C(＝O)O H H H2 5-CH3C(＝O)O H H H 3 5-CH3C(＝O)O H H H 4 5-CH3C(＝O)O H H H 5 5-CH3C(＝O)O H H H 6 5-CH3C(＝O)NH H H H 0 5-CH3C(＝O)NH H H H 1 5-CH3C(＝O)NH H H H 2 5-CH3C(＝O)NH H H H 3 5-CH3C(＝O)NH H H H 4 5-CH3C(＝O)NH H H H 5 5-CH3C(＝O)NH H H H 6 5-CH3NHC(＝O) H H H 0 5-CH3NHC(＝O) H H H 1 5-CH3NHC(＝O) H H H 2 5-CH3NHC(＝O) H H H 3 5-CH3Table 19-NHC (═ O) H45-CH3NHC(＝O) H H H 5 5-CH3NHC(＝O) H H H 6 5-CH3C(＝O)O H H H 0 3-Cl，5-CF3C(＝O)O H H H 1 3-Cl，5-CF3C(＝O)O H H H 2 3-Cl，5-CF3C(＝O)O H H H 3 3-Cl，5-CF3C(＝O)O H H H 4 3-Cl，5-CF3C(＝O)O H H H 5 3-Cl，5-CF3C(＝O)O H H H 6 3-Cl，5-CF3C(＝O)NH H H H 0 3-Cl，5-CF3C(＝O)NH H H H 1 3-Cl，5-CF3C(＝O)NH H H H 2 3-Cl，5-CF3C(＝O)NH H H H 3 3-Cl，5-CF3C(＝O)NH H H H 4 3-Cl，5-CF3C(＝O)NH H H H 5 3-Cl，5-CF3C(＝O)NH H H H 6 3-Cl，5-CF3C(＝O)N(CH)3H H H 0 3-Cl，5-CF3C(＝O)N(CH)3H H H 1 3-Cl，5-CF3C(＝O)N(CH)3H H H 2 3-Cl，5-CF3C(＝O)N(CH)3H H H 3 3-Cl，5-CF3C(＝O)N(CH)3HH H 4 3-Cl，5-CF3C(＝O)N(CH)3H H H 5 3-Cl，5-CF3C(＝O)N(CH)3H H H 6 3-Cl，5-CF3NHC(＝O) H H H 0 3-Cl，5-CF3NHC(＝O) H H H 1 3-Cl，5-CF3TABLE 19-CONTINUONHC (═ O) H H23-Cl, 5-CF3NHC(＝O) H H H 3 3-Cl，5-CF3NHC(＝O) H H H 4 3-Cl，5-CF3NHC(＝O) H H H 5 3-Cl，5-CF3NHC(＝O) H H H 6 3-Cl，5-CF3O H H H 0 3-Br，5-CF3O H H H 1 3-Br，5-CF3O H H H 2 3-Br，5-CF3O H H H 3 3-Br，5-CF3O H H H 4 3-Br，5-CF3O H H H 5 3-Br，5-CF3O H H H 6 3-Br，5-CF3S H H H 0 3-Br，5-CF3S H H H 1 3-Br，5-CF3S H H H 2 3-Br，5-CF3S H H H 3 3-Br，5-CF3S H H H 4 3-Br，5-CF3S H H H 5 3-Br，5-CF3S H H H 6 3-Br，5-CF3NH H H H 0 3-Br，5-CF3NH H H H 1 3-Br，5-CF3NH H H H 2 3-Br，5-CF3NH H H H 3 3-Br，5-CF3NH H H H 4 3-Br，5-CF3NH H H H 5 3-Br，5-CF3TABLE 19-NH H H63-Br, 5-CF3N(CH3) H H H 0 3-Br，5-CF3N(CH3) H H H 1 3-Br，5-CF3N(CH3) H H H 2 3-Br，5-CF3N(CH3) H H H 3 3-Br，5-CF3N(CH3) H H H 4 3-Br，5-CF3N(CH3) H H H 5 3-Br，5-CF3N(CH3) H H H 6 3-Br，5-CF3C(＝O)O H H H 0 3-Br，5-CF3C(＝O)O H H H 1 3-Br，5-CF3C(＝O)O H H H 2 3-Br，5-CF3C(＝O)O H H H 3 3-Br，5-CF3C(＝O)O H H H 4 3-Br，5-CF3C(＝O)O H H H 5 3-Br，5-CF3C(＝O)O H H H 6 3-Br，5-CF3C(＝O)NH H H H 0 3-Br，5-CF3C(＝O)NH H H H 1 3-Br，5-CF3C(＝O)NH H H H 2 3-Br，5-CF3C(＝O)NH H H H 3 3-Br，5-CF3C(＝O)NH H H H 4 3-Br，5-CF3C(＝O)NH H H H 5 3-Br，5-CF3C(＝O)NH H H H 6 3-Br，5-CF3C(＝O)NCH3H H H 0 3-Br，5-CF3C(＝O)NCH3H H H 1 3-Br，5-CF3C(＝O)NCH3H H H 2 3-Br，5-CF3C(＝O)NCH3H H H 3 3-Br，5-CF3TABLE 19-continuous C (═ O) NCH3H H H 4 3-Br，5-CF3C(＝O)NCH3H H H 5 3-Br，5-CF3C(＝O)NCH3H H H 6 3-Br，5-CF3NHC(＝O) H H H 0 3-Br，5-CF3NHC(＝O) H H H 1 3-Br，5-CF3NHC(＝O) H H H 2 3-Br，5-CF3NHC(＝O) H H H 3 3-Br，5-CF3NHC(＝O) H H H 4 3-Br，5-CF3NHC(＝O) H H H 5 3-Br，5-CF3NHC(＝O) H H H 6 3-Br，5-CF3O H H H 0 3，5-(CF3)2O H H H 1 3，5-(CF3)2O H H H 2 3，5-(CF3)2O H H H 3 3，5-(CF3)2O H H H 4 3，5-(CF3)2O H H H 5 3，5-(CF3)2O H H H 6 3，5-(CF3)2S H H H 0 3，5-(CF3)2S H H H 1 3，5-(CF3)2S H H H 2 3，5-(CF3)2S H H H 3 3，5-(CF3)2S H H H 4 3，5-(CF3)2S H H H 5 3，5-(CF3)2S H H H 6 3，5-(CF3)2NH H H H 0 3，5-(CF3)2TABLE 19-NH H H13, 5- (CF)3)2NH H H H 2 3，5-(CF3)2NH H H H 3 3，5-(CF3)2NH H H H 4 3，5-(CF3)2NH H H H 5 3，5-(CF3)2NH H H H 6 3，5-(CF3)2N(CH3) H H H 0 3，5-(CF3)2N(CH3) H H H 1 3，5-(CF3)2N(CH3) H H H 2 3，5-(CF3)2N(CH3) H H H 3 3，5-(CF3)2N(CH3) H H H 4 3，5-(CF3)2N(CH3) H H H 5 3，5-(CF3)2N(CH3) H H H 6 3，5-(CF3)2C(＝O)O H H H 0 3，5-(CF3)2C(＝O)O H H H 1 3，5-(CF3)2C(＝O)O H H H 2 3，5-(CF3)2C(＝O)O H H H 3 3，5-(CF3)2C(＝O)O H H H 4 3，5-(CF3)2C(＝O)O H H H 5 3，5-(CF3)2C(＝O)O H H H 6 3，5-(CF3)2C(＝O)NH H H H 0 3，5-(CF3)2C(＝O)NH H H H 1 3，5-(CF3)2C(＝O)NH H H H 2 3，5-(CF3)2C(＝O)NH H H H 3 3，5-(CF3)2C(＝O)NH H H H 4 3，5-(CF3)2C(＝O)NH H H H 5 3，5-(CF3)2Table 19-C (═ O) NH H63, 5- (CF)3)2C(＝O)N(CH3) H H H 0 3，5-(CF3)2C(＝O)N(CH3) H H H 1 3，5-(CF3)2C(＝O)N(CH3) H H H 2 3，5-(CF3)2C(＝O)N(CH3) H H H 3 3，5-(CF3)2C(＝O)N(CH3) H H H 4 3，5-(CF3)2C(＝O)N(CH3) H H H 5 3，5-(CF3)2C(＝O)N(CH3) H H H 6 3，5-(CF3)2NHC(＝O) H H H 0 3，5-(CF3)2NHC(＝O) H H H 1 3，5-(CF3)2NHC(＝O) H H H 2 3，5-(CF3)2NHC(＝O) H H H 3 3，5-(CF3)2NHC(＝O) H H H 4 3，5-(CF3)2NHC(＝O) H H H 5 3，5-(CF3)2NHC(＝O) H H H 6 3，5-(CF3)2Watch 20
R1＝
Figure A9711002501322
The preparation of intermediates in the preparation of the compounds of the present invention will now be described.
According to the chemical reaction scheme I, the compound represented by the formula VI and the compound represented by the formula [ III]can be prepared.
The reaction starting compounds in chemical reaction scheme I are commercially available or can be prepared according to the methods described in the following related documents:
chem. (journal of organic chemistry) 22, 2512,
am chem.soc. (american society of chemists) 74, 4087(1952),
J.Am.Chem.Soc.70，2656(1948)，
Chem.Lett.，1987，627
synth., (organic synthesis), IV15 (1963).
Chemical reaction scheme I
Figure A9711002501331
For the protecting groups in the above chemical reaction scheme I and other reaction schemes, the entire contents of the "protecting groups in organic Synthesis" publication written by Greene and Wuts, second edition, 1992, by John Wiley&Sons company, are incorporated by reference.
In the formula): the reaction is carried out under the same reaction conditions as in the above method C; d1，D2，D3Each represents a selectively removable protecting group (e.g., D)1Represents benzyl, D2Represents an acetyl group, D3Representing benzoyl) and the other symbols are as defined above.
Chemical reaction scheme II
Figure A9711002501341
In the formula R100Represents R1But not Q1The other symbols are as defined above for the reaction starting compounds in chemical scheme II, and can be prepared according to chemical scheme I
Figure A9711002501342
[ other symbols are as defined above]
Figure A9711002501343
((c)or(d))
Figure A9711002501344
Figure A9711002501345
Wherein the symbols are as defined above.
Wherein R in the compounds of formulae IV and V1Is R1 1(R1 1Represents R1Middle Q2Or Q3The compounds of (b) are intermediates for preparing the compounds of the present invention, which are commercially available or can be prepared according to the following chemical reaction schemes III and IV.
The aldehyde compound represented by the formula a-CHO, wherein a is as defined above, can be used in the reaction for producing the compound of the formula V, and the aldehyde compound can be commercially available or can be produced according to the method described in the following documents.
The formaldehyde of the furan is used as the raw material,
Zh.Org.Khim.11，1955
Tetrahedron，39，3881
chem. pharm. Bull, 28, 2846, etc
The thiophene-carboxaldehyde is a compound of thiophene,
Tetrahedron，32，1403
J.Org.Chem。41 2835
Zh.Obshch Khim，34，4010
bull, Soc, Chim, France, 479(1963), etc
The pyrrole-carboxaldehyde is a compound of pyrrole,
beilstein, 21, 1269, etc
The compound of the isothiazole formaldehyde is taken as a raw material,
J.Meditin.Chem.13，1208
J.Chem.Soc.，446(1964)
the pyrazole-carboxaldehyde is a compound of pyrazole-carboxaldehyde,
Chem.Ber.97，3407
j.chem.soc., 3314(1957), etc
The imidazole formaldehyde is used as a basic material,
J.Pharn.Soc.Japan，60，184
J.Amer.chem.Soc., 71, 2444, etc
The thiazole formaldehyde is used as the main raw material,
japanese laid-open patent publication No.59-206370
Chem.Ab.，62 7764d
Chem.Ber.，101，3872
The thiadiazole formaldehyde is a mixture of a thiadiazole formaldehyde,
U.S. Pat. No. 1,113,705
Chemical reaction scheme III
Wherein the symbols are as defined above
Chemical reaction scheme IVWherein each symbol is as defined above for compounds of formula X having formulae A-L4(wherein L4A compoundrepresenting a halogen atom such as chlorine, bromine, iodine atom, etc.), which is commercially available as an intermediate for preparing the compound of the present invention, may be prepared by the following method.
Chemical scheme V
Wherein A and L4As defined above
Compounds of formulae IX, XI, XIII, as intermediates for the preparation of the compounds of the invention, can be prepared according to the chemical reaction schemes VI to IX.
VI to IX
Chemical reaction scheme VI
Figure A9711002501392
Wherein all symbols are as defined above
*)J.Amer.Chem.Soc.33 440(1905)
Chemical reaction scheme VII
Figure A9711002501401
Wherein Ms represents methylsulfonyl; ts represents a tosyl group; d5Represents a protective group for an alcohol (e.g., benzoyl, etc.); d6A protecting group representing formyl (e.g., acetal, etc.); l represents a hydroxyl group or L1；R2，R3，R4，R5，R6，R7，r，X，L1And i is as defined above.
Chemical reaction scheme VIII)
Figure A9711002501411
(in formula XIII, R2＝R3＝R4＝H)
Wherein all symbols are as defined above
Compounds of formula XV can be prepared according to chemical scheme IX
Chemical reaction scheme IX
Figure A9711002501412
Wherein all symbols are as defined above.
The compounds of the present invention are very useful for controlling various harmful insects, mites and ticks, etc., as listed below.
Hemiptera:
plant hoppers such as rice planthopper, brown rice planthopper and white back rice planthopper, plant hoppers such as black tail and two-spotted black tail, plant hopper, plant bug, plant hopper, etc.
Lepidoptera:
plutella xylostella families such as Chilo meditation, Cnaphaloya oryza sativa, corn borer, Parapedisia tetrerella, Notarcha derogata and Indian rice meditation, noctuidae families such as Spodoptera litura, Spodoptera exigua, littoralis nocturnal, Oriental armyworm, cabbage looper, cutworm, cabbage looper, Trichoplusia ni, Heliothis armigera, Helicoverpa spp. and Earias spp.
The order of Diptera:
culex species such as culex pipiens and culex tritaeniorhynchus, aedes species such as aedes aegypti and aedes albopictus, anopheles species such as anopheles sinensis, chironomidae, muscidae such as housefly and stable fly, calliphoridae, sarcophagidae, stable fly belly. Flower flies such as seed and onion flies, the family of trypanosomatidae, the family of drosophilidae, the family of biting midges, the family of gadfly, the family of gnathidae, the family of stinging flies, the family of agromyzidae, and the like.
Coleoptera order:
the genus Leptosphaera such as corn rootworm beetle and Diaphania henryi, the family Tortoise such as scarab beetle and the family Tortoise beetle of rufctprea, the family weevilidae such as rice weevil, rice weevil and callosobruchus chinensis, the family Bacteroides such as Tenera flava and Saprolegnia cucurbita, the family Thielaceae (family Psammidae) genus Laurena such as Hippodamia solanacearum, Viginiotroputa, the family Thieladaceae, the family Changbicaceae, the family bovidae, the family Cryptopteridae, and the like.
From the order of the dictyoptera: german cockroach, smoky cockroach, american cockroach, brown cockroach, oriental cockroach, and the like.
From the order of thysanoptera:
frankliniella palmata, thrips hawaiiensis, etc
Hymenoptera:
formicaceae, wasp family, hornet family, phyllosnidae such as turnip leaf wasp, and the like.
Straight wing order:
mole cricket family, acrididae, and the like, siphonaptera, Purex irritans and the like,
and (3) pediculizing:
head lice, pubic lice, and the like.
Isoptera (termites):
rhinoceros, termites, and the like.
From the order Acarina:
plant parasitic nematodes, spider mites such as tetranychus gossypii, citrus golden melon, tetranychus gossypii and panonychus ulmi, gall mites such as tea orange gall mite and pileus mitis, livestock parasitic hard mites such as tiny cow mites, house dust mites, and the like.
The compounds of the present invention are also useful for controlling various harmful insects, mites, ticks and the like which are resistant to conventional insecticides and acaricides.
When the compound is used as an effective component of an insecticide/tick mite killer, other components can not be added.
The compounds of the present invention are typically formulated as cloudy sprays, emulsifiable concentrates, wettable powders, flowable concentrates, granules, dusts, aerosols, fumigants (mists) and toxic baits. These formulations are generally prepared by mixing the compounds of the invention with a solid carrier, a liquid carrier, a gaseous carrier or a bait, and, if desired, with surfactants and other adjuvants.
Each formulation usually contains at least 0.01 to 95% by weight of the compound of the invention as an active ingredient.
Solid carriers commonly used in the above formulations include finely divided or particulate clay materials such as kaolin, diatomaceous earth, synthetic hydrated silica, bentonite, Fubasami clay and acid clay; various talc, ceramics, and other inorganic materials such as sericite, quartz, sulfur, activated carbon, calcium carbonate, and hydrated silica; chemical fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride.
Liquid carriers useful in the present invention include water, alcohols such as methanol, ethanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and methylnaphthalene; aliphatic hydrocarbons such as hexane, cyclohexane, kerosene and gas oil; esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile and isobutyronitrile; ethers such as diisopropyl ether and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; halogenated hydrocarbons such as dichloromethane, trichloroethane and carbon tetrachloride; dimethyl sulfoxide, and vegetable oils such as soybean oil and peanut oil.
Examples of the gaseous carrier or propellant used in the present invention may include teflon gas, butane gas, liquefied petroleum gas, dimethyl ether and carbon dioxide.
The surfactants used in the present invention include alkyl sulfates, alkyl sulfonates, alkylaryl ethers and polyoxyethylene derivatives thereof, polyethylene glycol ethers, polyol esters and sugar alcohol derivatives.
Examples of adjuvants for use in the present invention include fixatives or dispersants, such as casein, gelatin, polysaccharides, such as starch, gum arabic, cellulose derivatives and alginic acid, lignin derivatives, bentonite, sugars and synthetic water-soluble polymers, such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acid.
Examples of the stabilizer used in the present invention may include PAP (isopropyl acid phosphate), BHT (2, 6-ditert-butyl-4-methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty oils and esters thereof, and bases used in poison baits include poison bait substances such as grain powder, vegetable oils, sugars and crystalline cellulose; anti-aging agents such as deca-butylated hydroxytoluene and nordihydrowoundwood acid; preservatives, such as dehydroacetic acid; substances for preventing eating by mistake, such as chili powder; attractant flavors, such as cheese flavors or onion flavors.
The above formulations can be used as such or after dilution with water or together with other insecticides, nematicides, acaricides, bactericides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers and/or animal feeds in a non-mixed or premixed manner.
Examples of the insecticidal, nematicidal and/or acaricidal agents include organophosphorus compounds such as mediben [ O, O-dimethyl O- (3-methyl-4-nitrobenzophenone) phosphorothioate, bis [ 2-bromo-2-fenthion-2-fenprophen-2-oxo-2-fenprox-2-oxo-2-oxanilino-2-oxadiazine-2-fenthion-2-fenprophen-2-carboximidoyl-2-ethyl-2-carboximidoyl-2-ethyl-2-oxadiazine-2-bis [1, 3-2-bis [ 2-bromo-2-chloro-2-ethyl-2-phosphono-2-oxo-2-oxadiazine]propan-2-bromo-2-oxadiazine-2-bromo-2-oxadiazine-2-oxo-2-carboximidoyl-2-carboximidoyl-2-bis [1, 3-bis [1, 6-bis [1, 2-bis [ 2-ethyl]oxadiazine, 2-bis [ 2-bis [1, 2-ethyl]oxadiazine, 3-2-bis [1, 6-bis [1, 3-bis [1, 2-bis [1, 6-bis [1, 2-ethyl]phosphinyl]phosphinothioyl]phosphinyl]phosphinothioyl-2-6-2-bis [1, 6-ethyl]phosphinothioyl]oxadiazine, 2-bis [ O-2-6-2-bis [1, 6-bis [1, 2-bis [1, 6-bis [ 1-bis [ O]phosphinothioyl]phosphinyl]phosphinothioyl]phenoxy]phenyl]phosphinothioyl]phenoxy]phosphinothioyl]anil-2-6-2-6-2-6-2-6-bis [ 1-2-6-2-6-2-isopropyl-6-2-6-2-6-bis [ 1-2-6-2-bis [ 1-2-6-bis [ 1-6-bis [ 1-6-O]phosphinothioyl]oxadiazino-bis [ 1-6-O-6-bis [ 1-6-bis [ 1-6-bis [ 1-6-bis [ 1-methyl-bis [ 1-methyl-isopropyl-bis [ 1-6-O]phosphinothioyl]oxadiazino]phosphinothioyl]carbo-6-O]phosphinothioyl]anil-6-2-6-O-2-6-O-6-2-6-2-6-O]anil-6-2-6-2-6-2-6-bis [ 1-6-methyl-2-6-methyl-bis [ 1-methyl-bis [ 1-O]anil-methyl-2-6-methyl-2-6-methyl-6-bis [ 1-6-O-methyl-6-2-6-2-6-O]carbo-6-methyl-6-2-6-O]phosphinothioyl]carbo-6-O]carbo-6-2-methyl-O]carbo-6-2-6-bis [ 1-O]phosphinothioyl]carbo-6-fenthios-methyl-bis [ 1-6-methyl-6-methyl-O]carbo-6-2-O]phosphinothioyl]carbo-6-O-2-6-O]carbo-6-methyl-6-O]carboximino]phosphinothioyl]carbo-bis [ 1-2-O]carbo-O-6-fenthios]phosphinothioyl]carbo-2-6-O]phosphinothioyl]carbo-2-O-2-6-O-2-6-2-O-bis [ 1-O-2-6-2-oxadiazino-fenthios]carboximino]carbo-bis [ 1-O]phosphinothioyl]carbo-methyl-6-bis [ 1-6-O.
When the compound of the present invention is used as an active ingredient of agricultural insecticides and acaricides, the amount thereof to be used is usually 0.1 to 100 g per 10 acres. In the case of emulsifiable concentrates, wettable powders and flowable concentrates, these are used after dilution with water, the application concentrations usually being from 1 to 10,000 ppm. In the case of a granular or dusty material, it can be used without dilution.
When the compounds of the present invention are used as active ingredients of insecticides and acaricides for domestic use, they are usually formulated into emulsifiable concentrates, wettable powders and flowable concentrates. Diluting with water to obtain 0.1-500ppm solution; or the composition is prepared into oily spray, aerosol, fumigant and poison bait, and can be directly used without dilution.
Examples
Examples of the preparation, formulation and test of the compounds of the invention are described in further detail below, and these examples are not intended to limit the invention.
First we describe preparation examples of the compounds of the present invention.
Preparation example 1: preparation of Compound (1) by Process C
1.6 g of 4- (3- (4-chlorophenoxy) propoxy) -3, 5-dichlorophenoxyacetaldehyde diethylacetal (the preparation of the intermediate in preparation example 1 will be described later) was dropped into a mixture of 1 ml of hydrochloric acid and 9 ml of acetic acid at room temperature with stirring. After stirring at room temperature for 30 minutes, the above reaction solution was poured into ice water and extracted twice with 100 ml of diethyl ether. The ether layers were combined and washed with water, then twice with 5% aqueous sodium bicarbonate, then with water, and dried over anhydrous magnesium sulfate, followed by concentration to give 0.8 g of a crude product of 4- (3- (4-chlorophenoxy) propoxy) -3, 5-dichlorophenoxyacetal.
0.8 g of the above compound was dissolved in 5ml of diglyme and 0.59 g of triphenylphosphine was added. The reaction solution was stirred at 160 ℃ while dropping a solution prepared beforehand from 0.47 g of sodium chlorodifluoroacetate in 10 ml of diglyme (heated to 70 ℃). After stirring at 160 ℃ for 1.5 hours, the reaction solution was cooled to room temperature, poured into ice-water, and extracted twice with 100 ml of diethyl ether. The ether phase layers were combined and washed with water, dried over anhydrous magnesium sulfate, and concentrated to give a crude product. Chromatography of the crude product on silica gel gave 0.3 g of 4- (3-chlorophenoxy) propoxy) -3, 5-dichloro-1- (3, 3-difluoro-2-propenoxy) benzene.
Yield: 20 percent of
nD 25.5：1.5490
Preparative example 2-compound (5) was prepared using method C.
1.0 g of 4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-dichlorophenoxyacetal diacetal (the production of the intermediate in production example 1 will be described later) was dropped into a mixed solution composed of 1 ml of hydrochloric acid and 9 ml of acetic acid at room temperature with stirring. After stirring at room temperature for 20 minutes, the above reaction solution was poured into ice water and extracted twice with 100 ml of diethyl ether. The ether layers were combined and the ether phase layer was washed with water, then twice with 5% aqueous sodium bicarbonate, then with water, and dried over anhydrous magnesium sulfate, followed by concentration to give 0.7 g of a crude product of 4- (4- (4-trifluoromethyl) phenoxy) butoxy) -3, 5-dichlorophenoxyacetaldehyde.
0.7 g of the compound obtained above was dissolved in 20 ml of dichloromethane, and 1.1 g of tribromofluoromethane, 1.0 g of triphenylphosphine and 0.26 g of zinc were added, followed by stirring at room temperature for 12 hours. The solution was concentrated to give the crude product. Chromatography of the crude product on silica gel gave 0.34 g of 4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene.
Yield: 33 percent
nD 23.0：1.5339
Preparation example 3: preparation of Compound (6) by Process C
0.7 g of 4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-difluorophenoxyacetaldehyde prepared as described in the upper half of preparation example 2 and 0.8 g of zinc were added with stirring at 45 ℃ to 20 ml of tetrahydrofuran. To the above solution was added 0.8 g of (dichlorofluoromethyl) tris (dimethylamino) phosphine chloride [ this compound was prepared as follows: trichlorofluoromethane (2.5 g) was dissolved in 20 ml of diethyl ether, and then a solution composed of 2.2 g of tris (dimethylamino) phosphine and 10 ml of diethyl ether was added dropwise with stirring at 0 ℃. After stirring at 0 ℃ for 2 hours, the reaction temperature was raised to room temperature and further stirred for 20 hours, and the precipitated crystals were obtained by filtration to obtain 3.0 g of (dichlorofluoromethyl) tris (dimethylamino) phosphine chloride, followed by stirring at 60 ℃ for 5 hours, and the above-mentioned reaction solution was filtered, and the filtrate was concentrated to obtain a crude product, which was then separated by silica gel chromatography to obtain 0.24 g of about 4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene.
Yield: 25 percent of
nD 21.5：1.5209
The numbers of the compounds of the invention are described below, together with embodiments of the invention.
(1)4- (3- (4-chlorophenoxy) propoxy) -3,5-dichloro-1- (3, 3-difluoro-2-propenoxy) benzene, nD 25.5：1.5490
(2)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3-methyl-5-ethyl-1- (3, 3-difluoro-2-propenyloxy) benzene,
nD 25.5：1.4955
(3)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3, 5-dichloro-1- (3, 3-difluoro-2-propenyloxy) benzene, nD 25.5：1.5082
(4)4- (3-chlorophenoxy) -2-chloro-1- (3, 3-difluoro-2-propenoxy) benzene, nD 22.5：1.5643
(5)4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene, nD 23.0：1.5339
(6)4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene, nD 21.5：1.5209
(7)4- (4- (4- (chlorophenoxy) butoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene, nD 17.0：1.5654
(8)4- (4- (4- (chlorophenoxy) butoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenoxy) benzene, nD 17.0：1.5731
(9)4- (4- (4-bromophenoxy) butoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(10)4- (4- (4- (bromophenoxy) butoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(11)4- (4- (4-isopropoxyphenoxy) butoxy) 3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(12)4- (4- (4- (isopropoxy) phenoxy) butoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(13)4- (4- (4- (trifluoromethoxy) phenoxy) butoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(14)4- (4- (4- (trifluoromethoxy) phenoxy) butoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(15)4- (4- (4- (chlorophenoxy) butoxy) -3, 5-diethyl-1- (3-chloro-3-fluoro-2-propenoxy) benzene,
(16)4- (4- (4- (chlorophenoxy) butoxy-3, 5-diethyl-1- (3-bromo-3-fluoro-2-propenoxy) benzene,
(17)4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-diethyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(18)4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-diethyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(19)4- (4- (4- (isopropoxyphenoxy) butoxy) -3, 5-diethyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(20)4- (4- (4- (isopropoxyphenoxy) butoxy) -3, 5-diethyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(21)4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3-chloro-5-methyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(22)4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3-chloro-5-methyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(23)4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3-ethyl-5-methyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(24)4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3-ethyl-5-methyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(25)4- (4- (4- (isopropoxyphenoxy) butoxy) -3-ethyl-5-methyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(26)4- (4- (4- (isopropoxyphenoxy) butoxy) -3-ethyl-5-methyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(27)4- (3- (4-chlorophenoxy) propoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenoxy) benzene,
(28)4- (3- (4-chlorophenoxy) propoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenoxy) benzene,
(29)4- (3- (4-bromophenoxy) propoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(30)4- (3- (4-bromophenoxy) propoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(31)4- (3- (4-isopropoxyphenoxy) propoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(32)4- (3- (4-isopropoxyphenoxy) propoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(33)4- (3- (4- (trifluoromethoxy) phenoxy) propoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(34)4- (3- (4- (trifluoromethoxy) phenoxy) propoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(35)4- (3- (4-chlorophenoxy) propoxy) -3, 5-diethyl-1- (3-chloro-3-fluoro-2-propenoxy) benzene,
(36)4- (3- (4-chlorophenoxy) propoxy) -3, 5-diethyl-1- (3-bromo-3-fluoro-2-propenoxy) benzene,
(37)4- (3- (5-trifluoromethyl) -2-pyridyloxy) propoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
nD 17.51.5211
(38)4- (3- (5- (trifluoromethyl) -2-pyridyloxy) propoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
nD 17.51.5319
(39)4- (3- (4- (trifluoromethyl) phenoxyamino) propoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(40)4- (3- (4- (trifluoromethyl) phenoxyamino) propoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(41)4- (3-chloro-5- (trifluoromethyl) -2-pyridyloxy)-3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(42)4- (3-chloro-5- (trifluoromethyl) -2-pyridyloxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(43)4- (3, 5-bis (trifluoromethyl) -2-pyridyloxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(44)4- (3, 5-bis (trifluoromethyl) -2-pyridyloxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(45)4- (5- (trifluoromethyl) -2-pyridyloxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(46)4- (5- (trifluoromethyl) -2-pyridyloxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(47)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(48)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(49)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3, 5-diethyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(50)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3-ethyl-5-methyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(51)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3, 5-diethyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(52)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3-ethyl-5-methyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(53)4- (4- (4- (chlorophenoxy) butoxy) -3-ethyl-5-methyl-1- (3-bromo-3-fluoro-2-propenoxy) benzene,
(54)4- (4- (4- (chlorophenoxy) butoxy) -3-ethyl-5-methyl-1- (3-chloro-3-fluoro-2-propenoxy) benzene,
(55)4- (3- (5-trifluoromethyl) -2-pyridyloxy) propoxy)-3, 5-diethyl- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(56)4- (3- (5-trifluoromethyl) -2-pyridyloxy) propoxy) -3, 5-diethyl- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(57)4- (3- (5-trifluoromethyl) -2-pyridyloxy) propoxy) -3-hexyl-5-methyl- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(58)4- (3- (5-trifluoromethyl) -2-pyridyloxy) propoxy) -3-ethyl-5-methyl- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(59)4- (4- (4-chlorophenoxy) butoxy) -3-chloro-5-methyl-1- (3-bromo-3-fluoro-2-propenoxy) benzene,
(60)4- (4- (4-chlorophenoxy) butoxy) -3-chloro-5-methyl-1- (3-chloro-3-fluoro-2-propenoxy) benzene,
(61)4- (4- (4-isopropoxyphenoxy) butoxy) -3-chloro-5-methyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(62)4- (4- (4-isopropoxyphenoxy) butoxy) -3-chloro-5-methyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(63)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3-chloro-5-methyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(64)4- (3- (4- (trifluoromethyl) phenoxy) propoxy) -3-chloro-5-methyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
(65)4- (3- (5- (trifluoromethyl) -2-pyridyloxy) propoxy) -3-chloro-5-methyl-1- (3-bromo-3-fluoro-2-propenyloxy) benzene,
(66)4- (3- (5- (trifluoromethyl) -2-pyridyloxy) propoxy) -3-chloro-5-methyl-1- (3-chloro-3-fluoro-2-propenyloxy) benzene,
an example of the preparation of an intermediate represented by formula VII of the present invention will be described below.
Preparation of intermediates example 1
20 g of hydroquinone monobenzyl ether and 500 ml of carbon tetrachloride were introduced into a reactor, and then a solution of 22 g of tert-butyl hypochlorite and 20 ml of carbon tetrachloride was slowly dropped thereto while cooling with ice and stirring. After 24 hours of dropping, the reaction solution was poured into water, and an organic phase layer (carbon tetrachloride phase layer) was separated. The resultant was washed with water, dried over anhydrous magnesium sulfate, and then concentrated to obtain a crude product. 22.8 g of about 4-benzyloxy-2, 6-dichlorophenol was obtained by silica gel chromatography (yield: 85%).
To a mixture of 5.0 g of 4-benzyloxy-2, 6-dichlorophenol, 4.7 g of 1-bromo-3- (4-chlorophenoxy) propane and 30 ml of N, N-dimethylformamide was added 2.7 g of potassium carbonate with stirring at room temperature, and after stirring at room temperature for 12 hours, the above reaction solution was poured into ice-water and extracted twice with 200 ml of diethyl ether. The ether layers were combined and washed with water, and dried over anhydrous magnesium sulfate, followed by concentration to obtain a crude product. About 4-benzyloxy-1- (3- (4-chlorophenoxy) propoxy) -2, 6-dichlorobenzene (yield: 85%) was obtained 6.5 g by silica gel chromatography.
6.5 g of 4-benzyloxy-1- (3- (4-chlorophenoxy) propoxy) -2, 6-dichlorobenzene and 200 ml of ethyl acetate were charged into a reactor, the air in the reactor was replaced with nitrogen, then 0.5 g of 10% palladium on carbon was added, and the nitrogen in the reactor was replaced with hydrogen and vigorously stirred at room temperature for 8 hours. After replacement of the hydrogen with nitrogen. The reaction solution was filtered with celite, and the filtrate was concentrated to obtain 5.2 g of 4- (3- (4-chlorophenoxy) propoxy-3, 5-dichlorophenol (yield: 93%).
2.0 g of 4- (3- (4-chlorophenoxy) propoxyA mixture of 3, 5-dichlorophenol, 1.25 g of bromoacetaldehyde diethyl acetal, 0.95 g of potassium carbonate and 15 ml ofN, N-dimethylformamide is stirred at 100 ℃ for 8 hours. After completion of the reaction, the reaction solution was brought to room temperature, and after the solution was poured into ice water and extracted twice with 200 ml of diethyl ether, the ether layers were combined and washed with water, dried over anhydrous magnesium sulfate, and then concentrated to give a crude product, which was chromatographed on silica gel to give 2.0 g of 4- (3- (4-chlorophenoxy) propoxy-3, 5-dichlorophenoxyacetal diacetal (yield: 75%). 4- (3- (4- (chlorophenoxy) propoxy-3, 5-dichlorophenoxyacetal diacetal: nD 23.01.5402。
Embodiments of intermediates of formula III are described below
(1)2, 6-dichloro-4- (3-fluoro-3-chloro-2-propenyloxy) phenol
(2)2, 6-dichloro-4- (3-fluoro-3-bromo-2-propenyloxy) phenol
(3) 2-ethyl-6-methyl-4- (3-bromo-3-fluoro-2-propenyloxy) phenol
(4) 2-ethyl-6-methyl-4- (3-chloro-3-fluoro-2-propenyloxy) phenol
(5)2, 6-diethyl-4- (3-bromo-3-fluoro-2-propenyloxy) phenol
(6)2, 6-diethyl-4- (3-chloro-3-fluoro-2-propenyloxy) phenol
(7) 2-chloro-6-methyl-4- (3-bromo-3-fluoro-2-propenyloxy) phenol
(8) 2-chloro-6-methyl-4- (3-chloro-3-fluoro-2-propenyloxy) phenol
The following describes formulation examples in which "parts" are by weight and the compounds of the present invention are represented by the compound numbers thereof as described above.
Formulation example 1 emulsifiable concentrate
10 parts of each of the above-mentioned compounds (1) to (66) of the present invention were dissolved in 35 parts of xylene and 35 parts of N, N-dimethylformamide, and then 14 parts of polyoxyethylene styrene phenyl ether and 6 parts of calcium dodecylbenzenesulfonate were added. The respective mixtures were sufficiently stirred, and 10% emulsifiable concentrates of the above-mentioned respective compounds were prepared.
Formulation example 2 wettable powder
20 parts of each of the above-mentioned compounds (1) to (6) of the present invention was added to a good mixture consisting of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignosulfonate, 20 parts of synthetic hydrated silica powder and 54 parts of diatomaceous earth, respectively. The above mixture was stirred with a stirrer to form a 20% wettable powder of each of the above compounds.
Formulation example 3 granules
To 5 parts of each of the above-described compounds (1) to (66) of the present invention were added 5 parts of synthetic hydrated silica powder, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay, respectively. Each of the mixtures was then separately stirred and an appropriate amount of water was added, followed by further stirring, and granulated with a granulator, and then dried with air, to obtain granules of 5% of each compound.
Formulation example 4 dust agent
1 part each of the above-mentioned compounds (1) to (66) of the present invention was dissolved in an appropriate amount of acetone, and then 5 parts of synthetic hydrated silica powder, 0.3 parts of PAP and 93.7 parts of clay were added, and each mixture was stirred with a mixer, and acetone was evaporated off to obtain a 19% dust of each compound.
Formulation example 5 flowable agent
20 parts of each of the above-mentioned compounds (1) to (66) of the present invention were mixed with 1.5 partsof sorbitan trioleate and 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol. Each mixture was ground into fine particles having a particle size of not more than 3 μ with a sander and then 40 parts of an aqueous solution containing 0.05 parts of santonin and 0.1 parts of magnesium aluminum silicate was added, followed by 10 parts of propylene glycol. The mixtures were stirred well to produce a 20% water-based suspension of each compound.
Formulation example 6-oil spray
0.1 part of each of the above-mentioned compounds (1) to (66) of the present invention was dissolved in 5 parts of xylene and 5 parts of trichloroethane, respectively. This solution was then mixed with 89.9 parts of deodorized kerosene to prepare a 0.1% oil spray of each compound.
Formulation example 7-oil-based Aerosol
0.1 parts of each of the compounds (1) to (66) of the present invention was dissolved in 59.6 parts of deodorized kerosene together with 0.2 parts of tetramethrin, 0.1 parts of d-phenothrin, and 10 parts of trichloroethane, respectively, and then the above solution was put into an aerosol container equipped with a valve into which 30 parts of propellant (liquefied petroleum gas) was pressurized through the valve to form an oil-based aerosol of each compound.
Formulation example 8-Water-based Aerosol
50 parts of pure water was fed together with a mixture consisting of 0.2 parts of each of the compounds (1) to (66) of the present invention, 0.2 parts of d-allethrin, 0.2 parts of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosene and 1 part of emulsifier [ ATMOS300 (registered trademark of Atlas chemical Co)]into an aerosol container equipped with a valve through which 40 parts of propellant (liquefied petroleum gas) was pressurized into the container to form a water-based aerosol of eachcompound.
Formulation example 9-mosquito coil
First, each of the compounds (1) to (66) (0.3 g) of the present invention was mixed with 0.3 g of allethrin, and each mixture was dissolved in 20 ml of acetone, and then the above solutions were uniformly mixed with 99.4 g of mosquito coil support material (support material consisting of 4: 3 Tabu powder, pyrethrum residue powder, and wood powder) by stirring, and each mixture was kneaded with 120 ml of water, molded and dried to form a mosquito coil of each compound.
Formulation example 10-electric mosquito-repellent incense tablet
First, 0.4 g of each of the compounds (1) to (66) of the present invention, 0.3 part of d-allethrin and 0.4 g of piperonyl butoxide were dissolved in acetone to make the total volume 10 ml. Then, 0.5 ml of the above solution was uniformly absorbed on each 2.5cm × 1.5cm × 0.3cm substrate (a sheet prepared by forming a mixed fibrous material of cotton linter and paper pulp) for electric mosquito mat to form electric mosquito mat bodies of the respective compounds.
Formulation example 11-heated Aerosol formulation
First, 100 mg of each of the compounds (1) to (66) of the present invention was dissolved in an appropriate amount of acetone, and the above solutions were taken up in a 4.0 cm. times.4.0 cm. times.1.2 cm porous ceramic disk to form a heated aerosol preparation.
Formulation example 12 toxic bait
First, 10 mg of each of the compounds (1) to (66) of the present invention was dissolved in 0.5 ml of acetone, and then each of the above solutions was mixed with 5 g of a solid bait powder for poisoning animals (solid feed powder CE-2, trade name of Japanese clean corporation), and acetone was removed by air-drying to form a 0.5% toxic baitfor each compound.
The following test examples in which the compounds of the present invention are represented by the above-mentioned compound numbers show that the compounds of the present invention are useful as effective components of insecticides and/or acaricides.
Test example 1-insecticidal test against Spodoptera litura
2 ml of an emulsifiable concentrate of the test compound was diluted with 200 times of water (500ppm), the above concentrate was prepared according to formulation example 1 and put into 13 g of an artificial feed for spodoptera litura prepared in a polyethylene cup of 11cm diameter, 10 larvae of spodoptera litura of the fourth instar stage were put into the cup, and after 6 days, the larvae were observed to determine the mortality thereof, and this test was repeated twice.
The results showed that the compounds (1), (3), (5), (6), (7), (8), (37) and (38) of the present invention showed a mortality of 80% or more.
Test example 2-insecticidal test against Culex pipiens
The emulsifiable concentrate of the test compound prepared according to formulation example 1 was diluted with water, and then 0.7 ml of the above diluted solution was added to 100 mm of ion-exchanged water, in which the concentration of the active ingredient was adjusted to 3.5ppm, and 20 final-stage larvae were placed therein, and the mortality thereof was observed after 7 days, and the test results showed that the compounds (1), (6), (37) and (38) of the present invention exhibited a mortality of 100%.
Test example 3 insecticidal test on Aphis gossypii
A90-ml-capacity polyethylene cup was filled with sandy fertile soil and planted with cucumber seeds (Sagami Hanjiro), left in a greenhouse for 10 days, and seedlings at the first leaf stage were obtained, and 10 adult Aphis gossypii were placed on the seedlings, kept at a temperature of 25 ℃ and allowed to grow eggs over a day. Then, 25 ml of an emulsifiable concentrate of the test compound diluted with water (500ppm) prepared according to formulation example 1 was sprayed onto seedlings planted in the above-described cuppots. After standing for 6 days at 25 ℃, the number of live aphids was observed and counted. The results showed that the mortality of the compound (1) of the present invention was 100%.
Test example 4 insecticidal test against Plutella xylostella
The emulsified oil of the test compound prepared according to formulation example 1 at 200ppm was added to water containing a dispersant "Rino" (manufactured by Noyaku, Japan) to make a 0.1% (volume) solution, 25 ml of the above solution was sprayed onto cabbage of the fifth leaf stage, 25 ml per box, and the above treated plants were air-blasted. After 10 third instar larvae of plutella xylostella were placed on the above plants and tested for mortality after 4 days, the compounds (6), (7), (8), (37) and (38) of the present invention showed 100% mortality.
Test example 5 insecticidal test against Heliothis virescens
0.2 ml of a water dilution (100ppm) of the cream of the test compound prepared according to formulation example 1 was placed in 3 g of artificial feed placed in a 30 ml capacity plastic cup. The larvae of the tobacco budworm moth of the second instar were put in the above feed and the mortality thereof was measured after 6 to 7 days of the test in which 10 larvae were used for each group, the test results showed that the compound (5) of the present invention showed a mortality of 80% or more.

Claims (17)

1. A fluoropropene compound of formula I:
wherein R is1Represents:
C1-C10alkyl radical, C1-C5Haloalkyl, C2-C10Alkenyl radical, C2-C6Haloalkenyl, C3-C9Alkynyl, C3-C5Haloalkynyl group, C2-C7Alkoxyalkyl or C2-C7Alkyl thioalkyl or represents
C3-C6Cycloalkyl radicals, in which there may be C1-C4Alkyl radical, C1-C3Alkoxy or C1-C3Substituted by haloalkoxy; or represents
Can be covered with C1-C4C substituted by alkyl4-C9A cycloalkylalkyl group;
can be covered with C1-C4C substituted by alkyl5-C6A cycloalkenyl group;
can be covered with C1-C4C substituted by alkyl6-C8A cycloalkenylalkyl group; or Q of formula II1，Q2，Q3，Q4，Q5，Q6，Q7，Q8Or Q9，
Figure A9711002500031
Wherein A represents:
can be (R)16)qA substituted phenyl group, which is substituted,
can be (R)16)qSubstituted naphthyl, or
Can be (R)16)qSubstituted heterocyclic group, wherein q represents an integer of 0 to 7,
R16represents a halogen atom, a cyano group, a nitro group, a pentafluorothio group (F)5S)，(C1-C4Alkoxy) carbonyl, C1-C8Alkyl radical, C1-C3Haloalkyl, C1-C7Alkoxy radical, C1-C3Haloalkoxy, C1-C3Alkylthio radical, C1-C3Alkyl halidesThio radical, C1-C2Alkyl radicalSulfinyl radical, C1-C2Alkanesulfonyl group, C1-C2Halogenoalkylsulfinyl, C1-C2Haloalkanesulfonyl radical, C3-C6Alkenoxy radical, C3-C6Haloalkenyloxy, C2-C4Haloalkenyl, C2-C4Alkenyl radical, C2-C4Alkynyl, C2-C4Haloalkynyl group, C3-C6Alkynyloxy, C3-C6Haloalkynyloxy, C1-C3Hydroxyalkyl radical, C2-C4Alkoxyalkyl radical, C2-C4Alkylthio alkyl, amino, dimethylamino, acetylamino, acetyl, haloacetyl, formyl, carboxy, (C)1-C2Alkyl) aminocarbonyl, [ di (C)1-C2Alkyl) amino]Carbonyl group, C3-C6Cycloalkyl radical, C5-C6Cycloalkenyl radical, C3-C6Cycloalkoxy, or C5-C6A cycloalkenyloxy radical, or
Phenyl, phenoxy, benzyl or benzyloxy, wherein all of them may be substituted with at least one of the following substituents: a halogen atom, C1-C4Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy and C1-C3Haloalkoxy, or
When q is an integer of 2 to 5, two adjacent R16Linked at their terminal ends to form a trimethylene group, a tetramethylene group, a methylenedioxy group, which may be substituted by a halogen atom or C1-C3Alkyl radicals, or ethylenedioxy radicals,which may be substituted by halogen atoms or by C1-C3Alkyl substitution;
b represents an oxygen atom, S (O)nGroup NR14A group C (═ O) G, or a group GC (═ O), n represents an integer from 0 to 2, R14Represents a hydrogen atom or C1-C3An alkyl group;
g represents an oxygen atom or NR15，
R15Represents a hydrogen atom or C1-C3An alkyl group, a carboxyl group,
R5，R6，R7，R8and R9Each represents a hydrogen atom, C1-C3An alkyl group or a trifluoromethyl group, or a salt thereof,
R10and R11Each represents a hydrogen atom, C1-C3An alkyl group, a trifluoromethyl group or a halogen atom,
R12represents a halogen atom, C1-C4Alkyl radical, C1-C3Haloalkyl, C1-C3Alkoxy or C1-C3A haloalkoxy group which is a halogen atom,
R13represents a hydrogen atom, a halogen atom or a methyl group,
i represents an integer of 0 to 6,
j represents an integer of 1 to 6,
k represents an integer of 0 to 4,
l represents a number of 1 or 2,
m represents an integer of 0 to 2,
with the proviso that R1Does not represent 3, 3-dichloro-2-propenyl, 3, 3-dibromo-2-propanAlkenyl or 3-bromo-3-chloro-2-propenyl,
when A is can be (R)16)qWhen substituted naphthyl, R16Is not 3, 3-dichloro-2-propenyloxy, 3, 3-dibromo-2-propenyloxy or 3-bromo-3-chloro-2-propenyloxy,
when A is can be (R)16)qSubstituted Q1，Q3And Q6When it is phenyl, R16Is 3, 3-dichloro-2-propenyloxy, 3, 3-dibromo-2-propenyloxy or 3-bromo-3-chloro-2-propenyloxy, q ═ 1,
z represents an oxygen atom, a sulfur atom or NR17Wherein R is17Represents a hydrogen atom or C1-C3An alkyl group, a carboxyl group,
x represents a halogen atom, and X represents a halogen atom,
R2，R3and R4Each represents C1-C3Alkyl radical, C1-C3A haloalkyl group, a halogen atom or a hydrogen atom, r represents an integer of 0 to 2,
with the proviso that R2，R3And R4Not simultaneously representing a hydrogen atom.
2. A fluoropropene compound according to claim 1 wherein Z is an oxygen atom or a sulfur atom.
3. A fluoropropene compound according to claim 2 wherein R1Is Q1A is optionally substituted (R)16)qPhenyl substituted or may be substituted by (R)16)qSubstituted 2-pyridyl.
4. A fluoropropene according to claim 2 wherein R is1Is Q2A is optionally substituted (R)16)qPhenyl substituted or may be substituted by (R)16)qSubstituted 2-pyridyl.
5. A fluoropropene according to claim 2 wherein R is1Is Q3A is optionally substituted (R)16)qPhenyl substituted or may be substituted by (R)16)qSubstituted 2-pyridyl.
6. A fluoropropene according to claim 2 wherein R is1Is Q4，Q5，Q6，Q7，Q8Or Q9A is optionally substituted (R)16)qPhenyl substituted or may be substituted by (R)16)qSubstituted 2-pyridyl.
7. A fluoropropene compound according to claim 3 wherein Z is an oxygen atom, R is 0, R2And R3Not simultaneously representing a hydrogen atom.
8. A fluoropropene compound according to claim 4 wherein Z is an oxygen atom, R5，R6And R7Represents a hydrogen atom, i is an integer of 0 to 3, R is 0, R2And R3Not simultaneously representing a hydrogen atom.
9. According toThe fluoropropene compound of claim 5 wherein Z is an oxygen atom, R5，R6And R7Represents a hydrogen atom, i is an integer of 0 to 4, B is an oxygen atom, CO2Or CONH group, R ═ O, R2And R3Not simultaneously representing a hydrogen atom.
10. A fluoropropene compound according to claim 7, wherein X is a chlorine atom or a bromine atom.
11. A fluoropropene compound according to claim 8, wherein X is a chlorine atom or a bromine atom.
12. A fluoropropene compound according to claim9, wherein X is a chlorine atom or a bromine atom.
13. A fluoropropene compound which may be 4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene; 4- (4- (4- (trifluoromethyl) phenoxy) butoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene; 4- (4- (4- (chlorophenoxy) butoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene, 4- (4- (4- (chlorophenoxy) butoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene, 4- (3- (5- (trifluoromethyl) -2-pyridyloxy) propoxy) -3, 5-dichloro-1- (3-chloro-3-fluoro-2-propenyloxy) benzene, or 4- (3- (5- (trifluoromethyl) -2-pyridyloxy) propoxy) -3, 5-dichloro-1- (3-bromo-3-fluoro-2-propenyloxy) benzene.
14. An insecticide comprising the fluoropropene compound of any one of claims 1 to 13 as an active ingredient, and an inert carrier.
15. A method for controlling harmful insects, which comprises applying an insecticidal amount of a fluoropropene compound of any one of claims 1 to 13 to a locus where the harmful insects are propagated.
16. A compound having the formula III:
Figure A9711002500061
wherein R is2，R3，R4R and x are as defined in claim 1.
17. Use of a fluoropropene compound as claimed in any one of claims 1 to 13 as active ingredient for controlling harmful insects.
CN97110025.XA 1996-01-31 1997-01-30 Fluoropropene compound, insecticide containing the same and intermediate for production thereof Pending CN1167104A (en)

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